ES2210601T3 - PROCEDURE FOR OBTAINING TENSIOACTIVE GRANULATES. - Google Patents

Abstract

A method for the preparation of wash- and cleaning-active surfactant granules with bulk weights greater than 600 g/l by granulating surfactant formulations, comprises: (1) solutions of (A) alkyl benzene sulphonate (ABS) and/or alkyl polyglycoside (APG) surfactants and (B) carrier materials chosen from polycarboxylates or inorganic salts (preferably amorphous silicates) in a non-surfactant solvent are simultaneously nebulised through the same nozzle ; and (2) the nebulised solutions are dried in standard dryers, preferably in fluidised bed dryers or a ring mixer dryer with a high rpm, during which the two liquids separate to leave the strongly hygroscopic and tacky active substance at least partially surrounded by the non-tacky carrier material. Also claimed are washing or cleaning agents with bulk weights greater than 600 g/l which contain either (i) more than 60 wt.% ABS, (ii) more than 60 (70) wt.% APG or (iii) at least 10 (20) wt.% end product of the above method.

Description

Procedure for obtaining granules of surfactants

The invention relates to a method for obtaining granules of concentrated surfactants with active substance content above 45% by weight, referred to the granulate, which have a low hygroscopicity, a capacity clearly improved silage and high bulk weight.

The economical manufacture of powders light colored surfactants, especially surfactants anionic sulfate-based fatty alcohols (FAS) and alkylbenzenesulfonates (ABS), is currently a state assured of industrial knowledge. The corresponding salts of surfactants are obtained in this case in forms of aqueous preparations, being able to adjust the water contents in the range from about 20 to 80% by weight and, especially, from about 35 to 65% by weight. The products of this type have, at room temperature, a pasty characteristic until able to be cut, being limited at room temperature the spreading and pumping capacity of such pastes already in the range of about 50% of substance active or this ability is lost in such a way that, during the storage and further processing of such pastes, especially during incorporation in mixtures, for example in washing and cleaning agents, problems arise considerable. Therefore it is an old necessity to put disposal washing agents in dry form, especially spreadable It is also really achieved, through technology conventional for drying, especially in drying towers, obtaining dispersible surfactant powders, for example spreadable FAS powders. In this case they are presented however serious limitations that especially question the economy of Industrial use of powders obtained in this way. The surfactant powders, dried through the tower present, frequently, very low bulk weights so that during the packaging and marketing of these powders are presented unprofitable conditions or such powders have to be compacted by granulation to give heavier granules. Also in the case of the manufacture of tower powders, reasoning concerning occupational safety may necessitate a Tower drying work form, limited in such a way that They present practical difficulties. In this way they can present themselves for example scabs on the tower that lead to a brown coloration of dust

Comparable difficulties and / or other difficulties they occur during the transformation of aqueous forms of preparation, especially pasty from another large number of surfactant compounds with washing and cleaning activity for give stable solid products to storage. By way of Example is necessary to obtain alkyl glycosides light colored, with washing and cleaning activity, in the field of the synthesis of a subsequent bleaching, for example with peroxide of aqueous hydrogen, so that in this case it also leads to forms of aqueous pastes with current technology. Such pasta Aqueous alkyl glycosides (APG pastes) are more threatened, for example by hydrolysis or by microbial impurities, which corresponding dry products. Also in this case the drying according to the technologies currently usual poses considerable difficulties. Finally, also the drying of an aqueous paste of alkaline salts of soaps with washing and / or paste activity ABS also poses considerable problems.

An alternative to spray drying of The surfactant pastes consist of the granulate. From this mode the EP-B-0 603 207 (Henkel) describes a process for the manufacture of granules of surfactants with washing and cleaning activity weighing a bulk above 500 g / l by granulation and drying simultaneous on all devices that can be taken to perform a granulation with simultaneous drying. In this case it granulate and, simultaneously, a form of preparation of dried surfactants, which has a non-surfactant liquid component (as a rule water), if desired with mixing of a solid component. The request does not indicate anything in relation to the ability to silage and the distribution of the active substance in the resulting grain, especially for the aptitude to surfactant extraction from the non-shredded product or shredded with the aid of non-aqueous solvents, not destroyers of grain. Also the simultaneous spraying through nozzles of the solution of the active substance and the support component, to through one and the same nozzle, represents in this case a possible parameter for the procedure, but that is not mandatory.

The task of the invention was to put provision a procedure for the manufacture of granules of heavy, dispersible, highly concentrated surfactants, with bulk weights above 600 g / l, presenting the granules Obtained advantages in terms of silage aptitude and hygroscopicity

The object of the invention is therefore a procedure for the manufacture of surfactant granules with washing and cleaning activity with bulk weights above 600 g / l by granulation of a preparation form of surfactants, characterized in that solutions are sprayed

to)

surfactants of alkylbenzenesulfonate and / or alkyl polyglycoside and

b)

materials of support chosen from the group consisting of polycarboxylates and by inorganic salts, especially silicates amorphous,

in a non-surfactant solvent, simultaneously, through one and the same nozzle and drying in traditional dryers, preferably in a fluidized bed in a annular mixer dryer with high number of solutions, having place during drying a separation between the two liquids of such way that the active substance sticky, strongly hygroscopic is partially embedded at least by the support substance not sticky

The process according to the invention has the advantage that the grains formed have, depending on the embedding of the surfactants phase in the material phase support, high mechanical stability and absorption of extraordinarily reduced heat during storage. The granules, obtained according to the process of the invention, are, therefore, spreadable and ensilable in a very good way and not they stick even in case of open storage depending on their Low tendency to absorb water. When the spraying by nozzles separated from the substance pastes active and support in the granulation unit, the product is already sticky with a low concentration of surfactant and scabs during drying, the products being hygroscopic and sticking in the course of strong water absorption.

The solutions of the active substance and the support substance is sprayed, according to the invention, through one and the same nozzle. In this case, the solutions in the nozzle, that is to say that they can lead to the nozzle through separate deposits and ducts, but also the mixing of both solutions can be sprayed through a nozzle from a single deposit.

The non-surfactant solvent, which may contain one or more components, has, under normal pressure, a point of boiling or a boiling range preferably by below 250 ° C and, especially, below 200 ° C. By way of Especially advantageous contains boiling components, under pressure normal, between 60 and 180ºC. As organic components, present in if necessary, the non-surfactant solvent will be used, preferably, mono and / or polyfunctional alcohols, for example methanol, ethanol, propanol, isopropanol, butanol, secondary butanol and tertiary, pentanol, ethylene glycol, 1,2-propanediol, glycerin or mixtures thereof. Preferably the proportion of mono and / or alcohols polyfunctional, used as a non-surfactant solvent, supposes from 0.5 to 10% by weight and, especially, from a 45 to 60% by weight, referred respectively to the shape of the surfactant preparation.

However, it will be used especially preferably water as an inorganic solvent component not surfactant, if appropriate together with such organic components such as ethanol, 1,2-propanediol or glycerin. In this In this case, the proportion of water is preferably 25 to 80% by weight, based on the total amount of solvent not surfactant The solutions of the surfactants and the Support materials in the non-surfactant solvent may be used in wide concentration intervals, having to take precautions only so that the viscosity is adequate still for a nozzle spray. In relation to whole of the solution, to be sprayed by nozzles, the proportion of the non-surfactant solvent amounts to 30 to 70% by weight and, especially, from 45 to 60% by weight.

As surfactants they will be used well alkyl benzenesulfonates (ABS) or alkyl polyglycosides (APG) or mixtures thereof. The alkylbenzenesulfonates preferably used they have a chain length of 9 to 13 carbon atoms, however, it is also possible, preferably, to Almost pure alkylbenzenesulfonates with 12 carbon atoms. The alkyl- or alkenylglycosides (APG) have, in general, the formula R-O- (G) x, in which R means a residue primary aliphatic, straight chain or methyl branched in the position 2, with 8 to 22, preferably with 12 to 18 atoms carbon, G is a symbol that represents a unit of glucose with 5 or 6 carbon atoms, and the average degree of oligomerized x is between 1 and 10, preferably between 1 and 2 and, especially, it is clearly less than 1.4.

Without harming the advantages of method according to the invention, in addition to the ABS and / or APG surfactants, also other anionic surfactants, not ionic, cationic or amphoteric in combination with those that have cited first. While the procedure is adequate, mainly for the manufacture of ABS motherboard mixtures and / or of APG, additions of up to 20% by weight of others are possible surfactants, relative to the total amount of surfactants without that in this case the advantages of the procedure according to the invention.

\hbox{(SiO _{2} ) _{m} (M _{2} O) _{n2} }

(H_{2}O)_{x}, donde M significa litio, sodio o potasio, m y n1 significan números enteros o fraccionarios mayores que 0, n2 significa 1 y x significa 0 o números enteros desde 1 hasta 20. Como solución de soporte para la granulación según el procedimiento de la invención se han acreditado especialmente soluciones de vidrios solubles. en los cuales M significa sodio y x significa 0 y cuyo módulo, es decir cuya relación m:n está comprendida entre 1,9 y 4, preferentemente entre 1,9 y 2,5. Las soluciones acuosas preferentes de vidrio soluble tienen en este caso contenidos en materia sólida del 1 al 80% en peso, preferentemente del 30 al 60% en peso.The support materials used in the process according to the invention can be of an inorganic nature and / or of an organic nature. In a preferred embodiment, they are constituted by amorphous alkaline silicates of the formula (SiO2) m (M2O) n1 (the so-called soluble glasses) and / or crystalline layered silicates

 \ {{SiO2) m (M2O) n2} 

(H 2 O) x, where M means lithium, sodium or potassium, my n1 means whole or fractional numbers greater than 0, n2 means 1 and x means 0 or whole numbers from 1 to 20. As a support solution for the granulation according to the process of the invention, specially soluble glass solutions have been accredited. in which M means sodium and x means 0 and whose modulus, that is whose ratio m: n is between 1.9 and 4, preferably between 1.9 and 2.5. Preferred aqueous solutions of soluble glass have in this case solid contents of 1 to 80% by weight, preferably 30 to 60% by weight.

Like other support materials, which are used alone or in combination with silicates in the form of solutions, inorganic salts or polycarboxylates come into consideration organic Among inorganic salts, it is especially preferred sodium carbonate, while as a polycarboxylate it is preferably use citric acid / citrate copolymers and / or of acrylic acid / maleic acid.

Surfactant granules with activity of washing and cleaning present, preferably on the granulate finished, contained in support materials from 10 to a 50% by weight. Since surfactant granules highly Concentrates are preferred for economic reasons, they are preferred content in support material below 40, especially below 30% by weight. In addition to the so-called glasses soluble, overdue, find application in the forms of Preferred embodiments of the invention are also the carbonate of sodium, acrylic acid / maleic acid copolymers, as well as trisodium citrate as support materials. They are also preferred mixtures of the support substances, especially carbonate / silicate mixtures as well as mixtures of citrate / silicate.

The form of preparation of the surfactants is granulate and dry, obtaining granulated particles according to the process of the invention, in which the active substance is partially embedded in the support substance. In this case it Drying means the partial or complete elimination of non-surfactant solvent. Preferably it will be eliminated almost by complete the non-surfactant solvent.

The manufacture of surfactant granules it can be carried out according to the process of the invention in all devices on which a granulate can be carried out Under conditions for drying. Examples in this regard are heaters and granulators, especially dryers annular mixers, with high revolutions such as Turbo dryer® type granulators (Vomm Signature device, Italy). In a preferred embodiment, the invention provides, however, that the combination of both stages of the procedure is carry out in a fluidized bed that runs in batches or from continuous way. It is especially preferred to carry out the process continuously in a fluidized bed. In this In the case of fluidization, the preparation of surfactants from a joint nozzle. The mixture of both liquid components until pasty of the preparation form of the surfactants can be carried out in this case already before the nozzle or the nozzle. The devices with fluidized bed employees preferably have perforated plates with some dimensions of at least 0.4 m. Bedding devices are preferred fluidized having a perforated plate with a diameter between 0.4 and 5 m, for example 1.2 m or 2.5 m. Without However, fluidized bed apparatus are also suitable which have a perforated plate with a diameter greater than 5 m. How perforated plate preferably a perforated plate or a Conidur dish (commercial product of the Hein & Lehmann Firm, Federal Republic of Germany). Preferably the method according to the invention at air speeds of fluidized between 1 and 8 m / s and, especially, between 1.5 and 5.5 m / s. The discharge of the granules from the bed fluidized is advantageously carried out by means of a grading size classification. This classification can be carried out for example with a sieving device or by medium of a counter-directed air stream (air from classification), which is regulated in such a way that they separate from the bed fluidized only particles from a certain size of the particles and minor particles are retained in the fluidized bed. In a preferred embodiment the air incoming is constituted by sorting, heated or not heated, and by the heated bottom air. The temperature of bottom air is included in this case preferably between 80 and 400 ° C, especially between 90 and 350 ° C. The air for him fluidized is cooled by heat loss and heat from evaporation of non-surfactant solvent components. In a particularly preferred embodiment of the temperature of the fluidized air, approximately 5 cm above the plate the bottom is 60 to 120 ° C, preferably 65 to 90 ° C and, especially, from 70 to 85 ° C. The outlet temperature of air is preferably between 60 and 120 ° C, preferably below 100 ° C and especially advantageous it is between 70 and 85 ° C. In the procedure, carried out according to the invention, the mixture of both is blown solutions, which together form the way of preparing the surfactants, through a nozzle in the fluidized bed, in that no other solid matter other than mass is found of departure. In the fluidized bed, which works so continuous, the preparation of dried surfactants acts as a support material or as a material germination. In this case the solvent components do not surfactant evaporate completely or completely, covering the superficially dried germs until completely dried, with other amounts of the surfactant preparation form applied in such a way that the support substance covers the active substance. This special constitution of the granulate, which can only be obtained by simultaneous spraying to through nozzles of the solution of the active substance and of the solution of the support material, through one and the same nozzle, is because the non-surfactant solvent, evaporated, drags I get support material during the evaporation process start from the newly condensed layer on the grain and deposit it on the surface during the evaporation of the grain.

The granulation according to the invention can a dusting agent is introduced into the fluidized bed, preferably zeolite or sodium carbonate - especially when alkylbenzenesulfonates are used as surfactants - for the maintenance of the fluidized granulation process. These dusting agents prevent granulation during tackiness of wet grains additionally and favor both fluidized and dried to give the desired product. For the manufacture of granules according to the process of the invention This variant can be advantageous, however it is not necessarily necessary for the realization of the invention.

Thus they result, according to the procedure of the invention, granules of surfactants that dissolve easily in cold water, without being hygroscopic. Granules they have high mechanical stability and therefore excellent spreading and silage properties. With organic solvents, that do not destroy the constitution of the grain, can be extracted by dissolution only small contents of active substance from the non-shredded granules, while from the crushed granules the substance can be extracted largely active

Surfactant granules with activity of washing and cleaning, manufactured according to the procedure of the invention, have bulk weights above 600 g / l. These are ideally suitable, as components for the manufacture of washing and cleaning agents preferably containing washing and cleaning agents for surfactant granules with washing and cleaning activity, manufactured according to procedure of the invention, in amounts above 10% in weight, especially in amounts above 20% by weight, referred to the whole washing and cleaning agent. For the transformation into washing agents with high bulk weight or for other special applications a bulk weight of the surfactant granules with washing and cleaning activity, applied according to the process of the invention, above 700 g / l, especially above 800 g / l.

Advantageously they can be manufactured according to the Process of the invention surfactant granules with washing and cleaning activity, whose total content, with relation to the whole of the granulate, is greater than 40% by weight. Surfactant contents above 50% by weight and, especially, above 60% by weight, they are preferred in this case. In the case of the manufacture of granules of alkylbenzenesulfonates (ABS) and alkyl polyglycosides (APG), are Preferred ABS content above 40% by weight, preferably above 50% by weight and, especially, by over 60% by weight, referred to the granulate while the APG content is preferably above 50% in weight, preferably above 60% by weight and, especially, above 70% by weight, based on the granulate.

The procedure is suitable for manufacturing of highly concentrated surfactant granules and presents especially then advantages when the surfactants to be elaborated be sticky in nature, as in the case of alkylbenzenesulfonates and alkyl polyglycosides. Obviously, others can also be used additionally surfactants, which do not have adherent properties or properties widely unadherent. In this case it is preferred however the proportion of the other surfactants does not exceed 20% in weight, based on the total surfactant content, in the granules according to the invention.

Examples

By specific spraying through nozzles, aqueous solutions of surfactants and material support, through a nozzle with several channels in a dryer fluidized bed mother mixtures were obtained with the following composition:

TABLE 1 Composition [% by weight]:

E1 E2 E3 E4 E5 E6 E7 E8 ABS Four. Five - - - 60 fifty - 61 APG - 67 80 fifty - - 62 - Silicate twenty-one 22 17.5 10 13 fifteen - - Sokalan CP5® - - - - - - 33 - Citrate from sodium - - - - - - - 14 Carbonate from sodium 28 - - 35 - - - - Zeolite - - - - 22 30 - twenty Water 6 eleven 2.5 5 5 5 5 5 Weight to bulk 632 641 612 651 702 734 611 633 [g / l]

Sokalan CP5® is an acid copolymer Acrylic-maleic acid of the Firm BASF.

To show that a large part of the surfactant is embedded in the support material, tested a sample of E2 by liquid chromatography. When E2 was taken directly from production, presented, by extraction with methanol, an active substance content of 23% by weight, while that a test of the same charge gave, after shredded in the mortar an active substance content of 65% by weight when proceeded in the same way.

The solubility of E1 and E2 was determined respectively 5 g of the agent are disposed in a 1-container liter, in which 500 ml of demineralized water were found, which stirred by means of a propeller stirrer with a number of revolutions of 900 revolutions / minute. Conductivity is detected by means of a cell for the conductivity measurement and recorded on a chart. The measure was carried out until an increase could no longer be detected. The time to reach the constant conductivity of the agent was taken as 100%, the others corresponding solubility times were determined by calculation.

TABLE 2 Solubility test.

E1 E2 95% dissolved [minutes] 2.59 2.57 90% dissolved [minutes] 2.27 2.25 80% dissolved [minutes] 1.45 1.48 Residue at the end 1.5 minutes [% in weight] two 5 Residue after 5 minutes [% by weight] 0 0.

All mother mixes E1 to E8, manufactured according to the invention, they can be stored in the air without sticking in This case or without suffering its spreading capacity. An essay comparative between E5 and a comparable ABS stock mix, which can be acquired commercially, with a bulk weight of 400 g / l, and with an active substance content of 85% by weight gave, after 8 Storage hours (relative humidity 55%) values following:

TABLE 3 Hygroscopicity (storage test for 8 hours).

E5 Comparative Absorption of water [own weight in% in weight] 5 twenty Observations spreadable stickiness.

ABS / APG stock mixes, manufactured according to the invention are ideally suited as additives for washing agents since they provide agents with a enhanced solubility

When they didn't spray through one and the same nozzle solutions of the active substance and the substance of support, but they were sprayed through two separate nozzles, no spreadable granules with high bulk weight were obtained. On the contrary such mixtures were already stuck in the mixer to give viscous masses until pasty, which could no longer dry Additionally.

Claims (12)

1. Procedure for the manufacture of surfactant granules with washing and cleaning activity with bulk weights above 600 g / l by granulation of a form of preparation of the surfactants, characterized in that solutions are sprayed a) alkylbenzenesulfonate and / or of surfactants alkyl polyglycoside and b) support materials, chosen from the group formed by carboxylates and inorganic salts, especially of amorphous silicates, in a non-surfactant solvent, simultaneously through one and the same nozzle and dried in dryers traditional, preferably in a fluidized bed or in a annular mixer dryer with high speed, taking place, during drying, a separation between the two liquids, so that it is embedded at least partially the sticky active substance, strongly hygroscopic, by the non sticky support substance. 2. Method according to claim 1, characterized in that mono and / or polyfunctional alcohols are used as non-surfactant solvents, preferably in amounts from 0.5 to 10% by weight, based on the whole solution to be sprayed through the nozzle 3. Method according to one of claims 1 or 2, characterized in that water is used as a non-surfactant solvent, preferably in amounts from 25 to 80% by weight, based on the total amount of the non-surfactant solvent. 4. Method according to one of claims 1 to 3, characterized in that, for the maintenance of the fluidized bed granulation process, a dusting agent, preferably zeolite or sodium carbonate, is continuously introduced into the fluidized bed. 5. Method according to one of claims 1 to 4, characterized in that a silicate / citrate mixture is used as the support material. Method according to one of claims 1 to 5, characterized in that the content of the alkylbenzenesulfonate (ABS) of the surfactant granules with washing and cleaning activity is above 40% by weight, preferably above 50% by weight. weight and, especially above 60% by weight, referred to the granulate. 7. Method according to one of claims 1 to 6, characterized in that the alkyl polyglycoside (APG) content of the surfactant granules with washing and cleaning activity is above 50% by weight, preferably above 60% by weight and, especially, above 70% by weight, referred to the granulate. Method according to one of claims 1 to 7, characterized in that the total surfactant content of the surfactant granules with washing and cleaning activity is above 40% by weight, preferably above 50% by weight and , especially, above 60% by weight, based on the granulate. Method according to one of claims 1 to 8, characterized in that the surfactant granules with washing and cleaning activity contain up to 20% by weight of other surfactants, based on the amounts of ABS and APG. 10. Surfactant granules with activity of washing and cleaning with a bulk weight above 600 g / l, manufactured by a method according to one of the claims 1 to 9, containing more than 60% by weight in alkylbenzenesulfonate. 11. Surfactant granulate with activity of washing and cleaning with a bulk weight above 600 g / l, manufactured by a method according to one of claims 1 to 9, which contains more than 60% by weight, preferably more than 70% in weight in alkyl polyglycoside. 12. Washing and cleaning agent, which contains at least 10% by weight, preferably at least 20% by weight of a product of the process according to claims 1 to 9.