NO802171L - PROCEDURE FOR THE PREPARATION OF A DETERGENT AND CLEANER - Google Patents

Description

As is well known, detergents and cleaning agents used in the household, in commercial laundries and in industrial companies often contain large amounts of condensed phosphates,

especially tripolyphosphate, which is largely responsible for the good cleaning effect of these agents. The phosphate content of these agents is criticized in connection with questions about ecology, and thereby the opinion is also often represented that these phosphates enter rivers and lakes via the water to the water's eutrophication, i.e. leading to an increase in algae growth and oxygen consumption. Efforts are therefore made to remove the phosphate from washing and cleaning processes or from the funds used for that purpose or to significantly reduce its amount.

It is already known from DOS 1,617,058 to use water-insoluble cellulose derivatives, especially phosphorylated cotton in the washing process to soften the water.

However, this proposal is not a technically viable solution to the problem because often too large amounts of phosphorylated cotton must be added to bind the water's hardness formers, except that cellulose derivatives with little calcium binding capacity, such as e.g. sulfethoxycellulose, carboxymethylcellulose and succinic acid half-esters of cellulose.

It is further known from DOS 2,055,423 for powdered to granular detergents and cleaning agents to put insoluble, cation-exchanged net-formed polymers such as, for example, a net-formed polymer of divinylbenzene and polyacrylic acid or poly-metaerylic acid in water and in alkaline solutions. If you add these water-insoluble, in the form of fine particles, cation exchangers to the wash water, they are distributed each time in the textiles to be washed, and can only be rinsed out very incompletely. For this reason, it has also been proposed to add the granular polymers to the washing water in "sewn-in permeable bags. This, however, greatly limits the contact with the washing water

and thus the action of the polymer.

The invention relates to a method for producing a detergent and cleaning agent for washing, bleaching or cleaning solid materials, especially textiles. The method is characterized by the fact that an aluminum silicate that is synthetically produced contains bound water, a determination method specified in the description at 22°C has determined calcium binding capacity from 50 to 200 mg CaO/g anhydrous active substance with the general formula:

where Kat means a calcium-exchangeable cation of value n, x means a number from 0.7-1.5 and y a number from 0.8-6, preferably 1.3-4, and with a particle size between dust fineness and 100 u and preferably in the range from 50 to 1 m, as the particle size can also be below 10y, mixed as phosphate exchange substances in powder form with the other powdered substances of the product to be produced, or while stirring incorporates an aqueous mixture of water and heat -stable detergent- and cleaning agent-active substances, selected from the group consisting of surfactants, builders, foam stabilizers, dirt carriers, washing alkalis and optical brighteners, heat-dried on rollers or in an atomizing tower and thus transferred into a free-flowing powder and optionally mixing the thus-formed powder product with heat-resp. . moisture-stable active substances such as bleaches, non-ionic surfactants, odorants, enzymes, etc., the oily or pasty non-ionic surfactants or odorants being sprayed onto the powder.

The calcium binding capacity of aluminum silicates is preferably in the range from 100 to 200 mg CaO/g AS.

The cation is preferably sodium, but it can also be replaced with lithium, potassium, ammonium or magnesium, as well as with the cations of water-soluble organic bases, e.g. in the case of primary, secondary or tertiary amines or alkyl amines with a maximum of 2 C atoms per eel cooling rest or maximum 3-C atoms per alkylol residue.

The aluminosilicates defined above allow

be produced synthetically in a simple way 'e.g. by reaction'

of water-soluble silicates with water-soluble aluminates in the presence of water. For this purpose, aqueous solutions of the starting materials can be mixed with each other or a component

present in a solid state is reacted with the other component present as an aqueous solution. Also by mixing both components present in the solid state, the desired aluminum silicates are obtained in the presence of water. Aluminum silicates are also produced from AlCOH)^/ Al-203 or si°2^"ar ^et<=* vec^ reaction with the alkali silicate or aluminate solution. Finally, such substances are also formed from the smelting,-, however, this method seems to due to the necessary high melting temperatures and the necessity to transfer the smelting in finely divided products economically less interesting.

Admittedly, the cation-exchangeable aluminum silicates which can be used according to the invention only form when special precipitation conditions are observed, as otherwise products arise which do not have or have insufficient cation-exchange capacity. Production of the aluminum silicates usable according to the invention is discussed in the experimental part.

The aluminosilicates produced by precipitation or transferred by other methods in a finely divided state in aqueous suspension can be transferred from amorphous in the aged resp. in the crystalline state, however, there is hardly any difference between these two forms with regard to calcium binding capacity. Apart from the drying conditions, this is proportional to the amount of aluminum contained in the aluminum silicates. Nevertheless, the crystalline aluminum silicates are preferably used for the purpose according to the invention. The preferred calcium binding capacity, approximately in the range of 100-200 mg CaO/g AS, is found above all in compounds of the composition:

This sum formula comprises two types of different crystal structures (or their non-crystalline precursors), which also differ by their sum formula. This is:

The different crystal structures appear

in X-ray diffraction diagram, the d-values determined thereby are indicated below when discussing the production of the aluminum silicates.

The amorphous or crystalline aluminum silicates present in aqueous suspension can be separated from the remaining aqueous solution by filtration and dried at temperatures of e.g. 50-800°C. Depending on the drying conditions, the product contains more or less bound water. Anhydrous products are obtained at 800°C. If you want to expel the water completely, this is possible by heating for one hour at 800°C, in this way the AS content of the aluminum silicates is also determined.

Such high drying temperatures are not recommended for the aluminum silicates to be used according to the invention, it is appropriate not to exceed 400°C. It is a particular advantage that even at significantly lower temperatures of e.g.

80-200°C until removal of adhering liquid water dried products are usable for the purpose according to the invention. The aluminosilicates produced in this way, which contain varying amounts of bound water, appear after dividing the dried filter cake as a fine powder, the primary particle size of which is a maximum of 0.1 mm, but for the most part it is significantly lower and up to dust fineness, e.g. up to 0.1 y. In doing so, it must be taken into account that the primary particles may be agglomerated into larger structures. With many production methods, primary particle sizes in the range of 50-1 y are obtained.

With particular advantage, aluminum silicates are used, which consist of at least 80% by weight of particles of a size from 10 to 0.01 y, preferably from 8 to 0.1 y. Preferably, these aluminum silicates contain no primary or secondary particles over 40 y. In so far as it concerns crystalline products, these are referred to as "microcrystalline" for reasons of simplicity.

People have already been searching for a long time for a usable phosphate substitute that not only manages to bind calcium,

but also biologically can be broken down in the waste water. A wide variety of organic compounds have therefore been proposed as phosphate substitutes. The technical teaching according to the invention 'for this

purpose of using water-insoluble, cation-exchanged aluminum silicates is therefore completely opposite to the direction of work in the overall professional world. Thereby, it is particularly surprising that the water-insoluble aluminum silicates are completely rinsed from the textiles. The use of the aluminum silicates brings relief to the waste water in two respects: the amounts of phosphorus that enter the waste water are greatly reduced or eliminated, and the aluminum silicates do not require oxygen for biological degradation. They are of a mineral nature, eventually settle in treatment plants or in natural water and thus meet the ideal requirements for a phosphate substitute.

Preferably, water-soluble complexing or precipitating agents for calcium ions, whereby when using the process products the removal of contaminants is noticeably accelerated or improve. When using phosphorus-containing complexing or precipitating agents should, however, be selected in such quantities that the phosphorus load of the waste water is clearly less than when using the currently common detergents based on triphosphate.

For complexation or Precipitating agents include those of an inorganic nature such as e.g. pyrophosphate, triphosphate, higher polyphosphates and metaphosphates.

Organic compounds that tgene as complex; serings- or precipitants for calcium are found among polycarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids, carboxyalkyl ethers, polyanionic polymers, especially the polymeric carboxylic acids and phosphonic acids, these compounds being mostly used in the form of their water-soluble salts. ) Those as complex formers or precipitating agents for calcium ions, the aforementioned compounds are completely usable as builders, they can therefore be present in the agents produced according to the invention also in larger quantities than is necessary to fulfill their function as complex formers, j resp. precipitant for calcium ions.

The components of the process products which are preferably used as textile detergents or as household cleaning agents, especially the building materials, are mostly chosen so that the preparations react neutrally to strongly alkaline, so that the pH value of a 1% solution of a preparation is mostly in the range of 7-12. Thereby, e.g. the delicate detergent mostly neutral to slightly alkaline reaction (pH value = 57-9.5), while soaking, pre-wash and boiling detergents are more alkaline (pH value = 9.5-12, preferably 10 -11.5).If higher pH values are required for special cleaning purposes, this can be easily adjusted by using alkali silicates of a suitable Na 2 O : SiC 2 ratio or eth alkalis.

The washing, bleaching or cleansing agents which can also be used in the process for the production of washing and cleaning agents include e.g. surfactants, surfactant-like or non-surfactant-like foam stabilizers or inhibitors, textile softeners, neutrally or alkaline-reactive builders, chemically active bleaching agents, as well as stabilizers and/or activators for these. Other, mostly in smaller quantities, auxiliary substances and additives are e.g. corrosion inhibitors, antimicrobial substances, dirt carriers, enzymes, brighteners, dyes and fragrances, etc.

The composition of typical, according to the invention, manufactured at temperatures in the range from 50 to 100°C usable textile detergents lies in the range of the following recipe: 5-30% anionic and/or non-ionic and/or

zwitterionic surfactants

5-70% aluminum silicates (ref. to AS)

2-45% complex formers for calcium 0-50%■ washing alkalis that are not suitable for

complex formation (=alkaline building materials)

0-50% bleaching agents as well as other, mostly in smaller quantities, additives present in textile detergents.

According to the invention, the powdered aluminum silicates can therefore be easily mixed with the other detergent components, as oily or pasty products such as e.g. nonionics are sprayed onto the powder. Another manufacturing possibility consists in incorporating the powdered aluminum silicates into the other components of the agent present as aqueous slurry, which are then transferred into a powder by crystallization processes or by drying the water in the heat. After heat drying, e.g. on rollers or in an atomizing tower, it is then possible to incorporate heat- and moisture-sensitive components such as e.g. bleaching components and activators for these, enzymes, antimicrobial substances, etc.

Examples

The manufacture of the ready-made aluminum silicates to be used is first mentioned, as this manufacture is not covered by the invention.

in a vessel of 15 litres. content, the aluminate solution diluted with deionized water was mixed with the silicate solution under vigorous stirring. Both solutions were at room temperature. An X-ray amorphous sodium aluminum silicate was formed during the exothermic reaction as the primary precipitation product. After .10 minutes of vigorous stirring, the suspension of the precipitated product. transferred into a crystallization vessel, where it remained for some time at an elevated temperature for crystallization. After extracting the lye from the crystal slurry and washing with deionized water until the effluent wash water has a pH value of about 10, the filter residue was dried. If if you deviate from these general production regulations, this is emphatically mentioned in the special part. Thus, for example, in some cases for the application technical trials, the homogenised, non-crystallized suspension of precipitation products or the crystal porridge was used. The water content was determined by heating the product for one hour at 800°C.

In the production of microcrystalline aluminum silicates, characterized by the suffix "m", an aluminate solution diluted with deionized water was mixed with the silicate solution and treated with a high-speed intensive stirrer (10.00 0 rpm; make "Ultraturrax" from the company Janke og Kunkel IKA -Werk, Staufen/Breisgau/BRD). After ten minutes of vigorous stirring, the suspension of the amorphous precipitation product was transferred into a crystallization container, where the formation of large crystals was prevented by stirring the suspension. After suctioning off the lye from the crystal slurry and subsequent washing with deionized water until the drained wash water has a pH value of approx. 10, the filter residue is dried,

is then ground in a ball mill, divided into two fractions in an air power sieve (mikroplex-Windsichter from the company Alpine, Augsburg, BRD) into two fractions, the finer of which does not contain amounts above 10 y... The grain size distribution was determined by means of egg sedimentation weight.

The degree of crystallization. of an aluminum ilicate can be determined from the intensity of interference lines of an X-ray diffraction diagram of the eventual product compared to a corresponding diagram of X-ray diffraction resp. fully crystallized products.

All percentages are by weight.

The calcium binding capacity of the aluminum silicates was determined in the following way: 1 liter of an aqueous solution containing 0.594 g CaCl2 (=300 mg CaO/1 = 30°"dH) and with diluted NaOH at a pH value

of 10 set solution. mix with 1 g of aluminum silicate (ref. to AS). The suspension is then vigorously stirred for 15 ; minutes at a temperature of 22°C (- 2°C). After filtering off the aluminum silicate, the residual hardness x of the filtrate is determined. From this the calcium binding capacity is calculated in mg CaO/g. AS by formula: (30-x) . 10.

The calcium binding capacity is determined at higher ) temperatures, e.g. at 60°C, you always find better values than at 22°C. This circumstance distinguishes the aluminum silicates from most of the soluble complex formers proposed to date for use in the detergent and is, in their use, a special technical advance.

If the product thus formed is dried for one hour at -400°C, an aluminum silicate Ia of composition: 0.9 Na20 is obtained. 1 A1203. 2.04 SiO 2 . 2.0 H 2 O

(= 11.4% H2O)

which is likewise suitable for the purpose according to the invention.

This product can also be dewatered by post-drying (1 hour at 400°C) until the composition: 0.8 Na^O . 1 A1203 2.65 SiO 2 .0.2 H 2 O

This dewatering product Ila is likewise usable for the purpose according to the invention.

The aluminum silicates I and II show the following interference lines in the X-ray diffraction diagram:

It is possible that in the X-ray diffraction diagram not all of these interference lines appear, especially when the aluminum silicates are not fully crystallized. Therefore, for the characterization of these types, the most important d-values were characterized with a "(+)".

To prepare the potassium aluminum silicate, the lye was sucked off, the residue washed with water and slurried in an aqueous KCl-containing solution. After 30 minutes of heating at 80-90°C, it was filtered off and washed. Primary particle size of the above-mentioned aluminum silicate was in the range from 10 to 45 p.-

The particle size distribution of the above-mentioned microcrystalline products Im and lim, determined by sedimentation analysis, was in the following range:

Example

This example relates to a textile detergent which serves to show the improvement of the washing effect of a

.aluminosilicate-containing detergent by adding a complexing agent or precipitant for calcium ions. The detergent is prepared as follows: 50.1 parts of aluminum silicate Ia were mixed with:

22.1 parts sodium perborate tetrahydrate

4.2 parts of that event. complex former or

precipitant for calcium ions in the form of sodium salt and with

23.6 parts of a powder formed by hot atomization of the following | composition: 5.3 parts alkylbenzene sulphonate sodium salt

2.0 parts tallow alcohol ethoxylate

(with 14 mol Ad)

2.8 parts of a sodium soap of

C12~<C>22~fatty acid 2.5 parts, water glass Na20.3,3 Si021,2 parts carboxymethylcellulose sodium salt

1.7 parts magnesium silicate 2.1 parts sodium sulfate 6.0 parts water.

As a complex former or precipitant for calcium ions, the following substances were used in the form of their sodium salts. In addition, their reference value is indicated, which is a reference to the washing effect of the detergent in question.

x)

<x>) These two material samples had been prepared by polymerization of acrolein and treatment of the polymerizate according to Cannizaro in the presence of formaldehyde.

Claims (4)

1. Process for the production of a washing and cleaning agent with a content of a water-insoluble, finely divided aluminum silicate as well as at least one compound from the group of surfactants, builders and bleaching agents, thereby containing an exchange agent for partial or complete replacement of condensed phosphates, characterized in that a synthetic produced aluminum silicate containing bound water and which, according to the description, has a determined determination method at 22°C calcium binding capacity of 50 to 200 mg CaO/g anhydrous active substance and with the general formula: wherein Kat means a calcium exchangeable cation of value n, x means a number from 0.7-1.5 and y means a number from 0.8-6, preferably 1.3-4 and with a particle size between dust fineness and 100 y and preferably in the range from 50 to 1 y, as the particle size can also be below 10 y, mixed as a phosphate exchange agent in powder form with the other components of the product to be produced, namely preferably incorporated into an aqueous mixture of water and heat stable detergent- and cleaning agent-active substances selected from the group consisting of surfactants, builders, foam stabilizers, dirt carriers, washing alkalis and optical brighteners, this mixture is transferred by crystallization or by heat drying on rollers or in an atomizing tower into a free-flowing powder, and possibly mixed, the thus formed powder product with heat or moisture-labile active substances, such as e.g. bleaches, non-ionic surfactants, odorants, enzymes, etc., by spraying the oily or pasty non-ionic surfactants or odorants onto the powder. 2. Method according to claim 1, characterized in that crystalline or X-ray amorphous aluminum silicates of composition are used: where Kat means ethyl alkylation, especially of sodium and n = 1. 3. Method according to claims 1 and 2, characterized in that aluminum silicates of composition are used: in that these aluminum silicates in the X-ray diffraction diagram have the following d-values (in X): 12.4 8.6 7.0 4.1 3.68 3.38 3.26 2.96 2.73 2.60. 4. Method according to claims 1 and 2, characterized in that aluminum silicates of composition are used: which in the X-ray diffraction diagram have the following d-values (in Å): 14.4 8.8 4.4 3.8 2.88 2.79 2.66.