RU2756808C2 - Use of waste from extraction and/or enrichment of non-metallic minerals containing layered silicates as components of detergent - Google Patents

Abstract

FIELD: detergents.

SUBSTANCE: invention relates to the use of waste from the extraction and/or enrichment of non-metallic minerals containing layered silicates, bentonite, and/or saponite as components of a detergent.

EFFECT: detergents containing in their composition waste from the extraction and/or enrichment of non-metallic minerals containing layered silicates have good washing properties.

1 cl, 33 ex, 3 tbl

Description

The invention relates to the chemical industry, in particular to detergents and cleaning agents for industrial and household purposes.

The use of sodium tripolyphosphate as a component of a detergent is widely known (see, for example, patents of Ukraine No. 1979, 3358).

However, tripolyphosphate, as a component of detergents (MS), has the following disadvantages: an active negative PR campaign is being conducted against it, about the dangers of phosphates, which is fundamentally wrong. But the consumer is already accustomed to the idea of the irreparable harm of phosphates, and the presence of phosphates in the composition of the MC has a huge negative impact on the promotion of the product on the market.

It is also known to use zeolites as a component of detergents, which are devoid of the disadvantages inherent in tripolyphosphate, for example, patent of Ukraine No. 13032.

However, zeolites are not layered silicates. It is known from scientific and technical literature that zeolites, as components of detergents, are effective for calcium hardness of water. This narrows the scope of their application.

Relatively recently, it has been proposed to use layered silicates as components. But layered silicates are effective for magnesium hardness, and somewhat less suitable for controlling calcium hardness.

Detergents containing zeolites are widely available on the market and their disadvantages are well known to manufacturers. In order to increase the detergency of zeolites and layered silicate compositions, manufacturers have to include various additives in detergents.

MC compositions contain a zeolite or layered silicate component, or a mixture thereof. The content of the component of the zeolite and / or layered silicate can be varied within wide limits, depending on the end use of the composition and its desired state of aggregation. Detergent compositions should include at least about 10% of such a component.

Liquid formulations typically include from about 5 to about 60 wt. %, more preferably from about 5 to about 30 wt. % component. Granular formulations typically include from about 10 to about 80 wt. %, more preferably from about 15 to about 50 wt. % component. However, it is understood that a decrease or increase in the content of the component is not excluded. Preferably, the weight ratio of the component or layered silicate or mixture thereof to the polyoxyalkyl fatty acid amide ranges from about 1:10 to about 20: 1, more preferably from about 1: 5 to about 15: 1, most preferably from about 1: 3 to about 10: 1.

Zeolite components are a class of aluminosilicate components that have gained momentum in heavy duty detergent formulations today, especially in granular formulations. The used components of the zeolite can be amorphous or crystalline in structure and can be of natural origin or synthetically obtained.

In addition, it is known to use as active components of detergents layered aluminosilicates of the montmorilonite group, called bentonites.

Bentonite - Al ₂ O ₃ (SiO ₂ ) ⋅H ₂ O, natural hydrated layered aluminum silicate. So far, the MS has used layered sodium silicates from numerous deposits around the planet, natural sodium bentonite or sodium montmorillonite. This type of layered silicate has found application due to its wide distribution in nature and the presence of extensive industrial deposits in the United States. They had a natural sodium structure, and therefore did not need additional modification to the sodium form (see, for example, the components of layered sodium silicate, US patent No. 4664839, registered on May 12, 1987).

Natural sodium bentonite (alkaline), like other silicates, as a component of a detergent, has a major drawback, these layered silicates are not waste, which means their price is much higher, and the detergent properties are much lower, but sodium bentonites have excellent gelation properties, calcium bentonites (alkaline earth) are more used in animal husbandry as an additive to feed, since their detergent properties are even lower. They are also used in washing powders as fillers and foam suppressants.

«светло-зеленый») - не слоистый минерал, водный алюмосиликат железа, кремнезема и оксида калия непостоянного состава, относится к группе гидрослюд.Glauconite (glauconite - "green earth", from ancient Greek.

"Light green") - not a layered mineral, water aluminosilicate of iron, silica and potassium oxide of variable composition, belongs to the group of hydromica.

The significant content of potassium oxide and the ability to easily succumb to weathering makes it a good fertilizer, it is also used as a raw material for the production of complex potash-phosphorus fertilizers. It is also used as a raw material for the manufacture of green paints for painting and industry. A good sorbent used for water purification, including the removal of heavy metal salts. Due to its cation exchange capacity, it is used to reduce the hardness of water. Its detergent properties are not significant at all.

Palygorskite is an aqueous magnesium aluminosilicate, the approximate chemical formula is Mg ₅ H ₂ [Si ₈ O ₂₂ ] (H ₂ O) ₆ × 2 (H ₂ O). According to the crystal structure, it is an intermediate type between the so-called strip and layered silicates. It is used as an adsorbent for the purification and clarification of liquids (wine, juice, etc.) in the wine and food industries, has good gel-forming properties, as an adsorbent for the purification of fats and oils, in pharmaceuticals as a filler and adsorbent.

Wastes from the extraction of non-metallic minerals (according to the IMA classification = native) contain layered silicates and / or their enrichment wastes, can be used as soil softeners, soil deoxidizers and additives to animal feed, if the percentage of layered silicates in them is high enough.

For the efficient use of waste from the extraction of non-metallic minerals (according to the IMA classification = native) containing layered silicates and / or their enrichment wastes, the amount of layered silicates must be sufficient for their effective use in animal husbandry, land reclamation or as components of detergents.

All of the detergents known to the applicant using layered aluminosilicates have used specially mined silicates or derivatives thereof.

The claimed invention proposes the use of waste from the extraction of non-metallic minerals (according to the IMA classification - native) and / or waste of their enrichment, containing layered silicates as components of the detergent.

Their washing effect is due to the complex effect of all components and their synergistic action.

The basis of the invention is the task of finding the field of application of waste from the extraction of non-metallic minerals (according to the IMA classification - native) and / or waste of their enrichment, containing layered silicates, as detergent components that have good detergent properties, are available and cheap.

Such waste is a big problem for the mining industry. And they pose a man-made threat to humans and the environment.

The problem is solved by using waste from the extraction and / or enrichment of non-metallic minerals (NPI) containing layered silicates as components of detergents.

The concept of "waste" is divided into mining and / or beneficiation wastes due to the fact that when coal or saponite is mined, there is no beneficiation waste, since these minerals do not contain impurities in sufficient quantity to change their properties. And during the extraction of zeolites or bentonites, impurities can be contained from 10 to 50%, which greatly affects their properties, therefore, enrichment is needed, which means it is enrichment waste.

Waste from the extraction of non-metallic minerals and waste from their enrichment, containing layered silicates, are both liquid and solid, in the form of a suspension or in a pasty form. Waste from the extraction of non-metallic minerals and waste of their enrichment, containing layered silicates, can contain from 0.5% (when stripping) to 100% layered silicates (when extracting layered silicates, for example, the Dashukovskoye deposit), and layered silicates come in various forms. Such, for example, as magnesium, lithium, calcium or sodium forms, and different in structure: two-layer, three-layer, layered - tape.

Since during the extraction and enrichment of non-metallic minerals, the mining equipment captures the entire layer with all accompanying minerals, and during the enrichment of non-metallic minerals, only the non-metallic minerals themselves are separated, then a general mixture of rocks goes to waste, with all the minerals inherent in this deposit, which are not are the subject of extraction, but are waste. The technologies existing today do not allow economically efficient separation of the wastes from the extraction and processing of non-metallic minerals into all their constituent components. It happens that they are further enriched to remove one of the components from the waste, or a group of components, for example, rare earth metals, but they do not separate the waste until they are completely separated into all components, since this is not economically feasible. For this reason, the wastes of the extraction of non-metallic minerals and their enrichment wastes containing layered silicates may also include other minerals that are inherent in this deposit, as accompanying minerals in the main ore body and / or overburden minerals.

For example, samples taken from the waste of the Sokyrnitsa zeolite deposit showed the following waste composition:

mineral content, % layered silicates 72.2 quartz 18.8 calcite 3.8 dolomite 5.2

Samples taken from the waste of the Khmelnytsky glauconite deposit have the following waste composition:

mineral content, % layered silicates 42.2 quartz 38.8 calcite 15.8 glauconite 3.2

Samples taken from the waste of the Dashukovskoye palygorskite deposit have the following waste composition:

mineral content, % layered silicates 98 quartz 0.5 calcite 0.3 palygorskite 1,2

The given data cannot be limiting, due to the fact that when using wastes from the extraction and enrichment of non-metallic minerals, their composition can vary over a fairly wide range.

From the scientific, technical and patent literature, it is not known the use of waste from the extraction of non-metallic minerals (according to the classification of MA - native) and / or waste of their enrichment, containing layered silicates, as a component of detergents.

The preparation and use of wastes from the extraction of non-metallic minerals (according to the IMA classification - native) and waste of their enrichment containing layered silicates of the Sokyrnitsky zeolite deposit, the Khmelnitsky glauconite deposit and the Dashukovsky palygorskite deposit is confirmed by the examples below.

Example 1. A universal detergent was prepared for washing dishes and other items that do not absorb water, for washing in hot and cold water, using waste from the production of non-metallic minerals from the Sokyrnitsa deposit. The components were taken at the following ratio, wt. %:

waste from the extraction of non-metallic useful fossils (NPI) ten water 90

Example 2, 3 was carried out similarly to Example 1, but with different qualitative and quantitative ratios of components. The data are shown in Table 1.

Examples 4, 5. 6 illustrate the preparation of a means for washing hair using mining waste and / or waste from the NPI of the Sokyrnitsa deposit. The data are shown in Table 1.

Examples 7, 8, 9 illustrate the preparation of a product for skin care and cosmetics removal using mining waste and / or dressing waste from the NPI of the Sokyrnitsky field. The data are shown in Table 1.

Examples 10-12 illustrate the preparation of a universal detergent for washing dishes and other items that do not absorb water for washing in hot and cold water using mining waste and / or waste from the NPI of the Khmelnitsky field. The data are shown in Table 2.

Examples 13-15 illustrate the preparation of a hair wash using mining waste and / or waste from the NPI of the Khmelnitsky field. The data are shown in Table 2.

Examples 16-18 illustrate the preparation of a product for skin care and cosmetics removal using mining waste and / or refining waste from the NPI of the Khmelnitsky field. The data are shown in Table 2.

Examples 19-21 illustrate the preparation of a universal detergent for washing dishes and other items that do not absorb water, for washing in hot and cold water using mining waste and / or waste from the NPI of the Dashukovskoye field. The data are shown in Table 3.

Examples 22-24 illustrate the preparation of a hair wash using mining waste and / or waste from the NPI of the Dashukovskoye field. The data are shown in Table 3.

Examples 25-27 illustrate the preparation of a product for skin care and cosmetics removal using mining waste and / or refinery waste from the Dashukovskoye field. The data are shown in Table 3.

Example 28 A known Fairy detergent was used as a dishwashing detergent and other non-absorbent items for washing in hot and cold water.

Fairy detergent contains the following components:

- sodium laureth sulfate (anionic surfactant), as indicated on the package, contains 5-15%;

- lauramine oxide (nonionic surfactant); as indicated on the package less than 5%;

- polypropylene glycol (solvent);

- sodium chloride;

- perfume;

- polyethyleneimine ethoxylate propoxylate;

- phenoxyethanol (preservative);

- 1,3-cyclohexanedimethylamine (complexing agent);

- sodium hydroxide (saponification of fats);

- methylisothiazolinone (preservative);

- propylene glycol (solvent);

- dyes;

- limonene (perfume);

- linalool (perfume);

- water.

(see https://ru.wikipedia.org/wiki/Fairy).

Example 29. A well-known detergent was prepared from natural ingredients for washing dishes and other items that do not absorb water, for washing in hot and cold water, containing the following components, wt. %:

nonionic surfactants (sugar tensides) 3.0 amphoteric surfactants (cocamidopropyl bevaine) 3.0 anionic surfactants (fatty sulphate of coconut oil alcohol) 2.0 sodium citrate (citric acid) 5.0 sodium chloride (salt) 10.0 orange terpene 1.0 ionized water 76.0

The composition of this tool is indicated on the website.

http://ecovita.ua/index.php?route=product/product&path=65_59&product_id=51.

Example 30. Prepared a known means for washing hair containing the following components, wt. %:

plantapon 17.0 dehyton 5.15 lamesoft 2.0 plantasil 7.0 sage Distillate 10.0 purisoft 0.1 dissolvine 0.05 perfume fragrance 0.2 sodium hydroxide + NaOH 0.1 aqua 58.4

The composition of the product is indicated on the website https://biakhim.com.ua/produkty/basf/syre-dlya-kosmetiki/plantacare-818-up file “natural composition for foam detergent formulations”.

Example 31. A known means for washing hair was prepared, containing the following components, wt. %:

birch bark extract (betulin) 0.05 PEG-150 polyglyceryl-2 stearate (PEG-: caprilic / capric glycerides) 0.50 glycerate-2 cocoate 2.60 lauryl glucoside carboxylate 0.80 sodium cocoamphomonoacetate 5.00 sodium cocoglutamate 2.20 glyceryl cocoate PEG-7 1.40 xanthan gum 0.2 allantoin 0.14 fir oil 0.08 palmarose oil 0.08 cocamidopropyl betaine 16.5 fresh birch sap 70.5

(see RF patent No. 2411934).

Example 32. A known agent for skin care and cosmetics removal was prepared, containing the following components by weight. %:

lauryl glucoside sodium carboxylate and lauryl glucoside 14.0 cocoglucoside 4.0 cocoamidopropyl betaine 4.0 guarhydroxypropyltrionium chloride 1.5 cocoglucoside and glyceryl oleate 1.5 ethanol 1.5 perfume fragrance 1.0 sanguinitrine derived from Macleay small-fruited 0.1 lemon acid 0.05 water 72.35

(see RF patent No. 2555358).

Example 33. A known agent for skin care and cosmetics removal was prepared, containing, by weight. %:

suffopon 6.0 plantacare 7.2 lamesoft 3.0 lavandula augustifola 20.0 sodium benzoate 0.5 citric acid 5.2 NaCl 0.2 aqua 57.9

(see https://biakhim.com.ua/produkty/basf/syre-dlya-kosmetiki/plantacare-818-up file "natural composition for foaming formulations").

All examples are given only to illustrate the comparative qualities of the detergent component and are not restrictive.

Studies of the detergent properties of the compositions according to examples No. 1, 2, 3, 10, 11, 12, 19, 20, 21, 28 and 29 were carried out according to the following procedure.

To study the detergent action in cold and hot water, an experiment was carried out to cleanse porcelain plates from fat (0.5 ml of sunflower oil was applied to each plate). For washing, standard dish sponges were used, on which 0.5 ml of the product and 10 ml of water of various temperatures (cold and then hot) were applied.

In the cases of examples No. 1, 2, 3, 10, 11, 12, 19, 20, 21, 28 and 29, all the compositions showed the same washing ability, which suggests that for washing dishes and surfaces that repel water, it is possible to waste mining non-metallic minerals and their enrichment wastes containing layered silicates, to introduce or not to introduce additional substances, they qualitatively remove pollution both with and without them. But due to their more diverse composition, they also have cleaning properties without introducing special components with cleaning properties into detergents.

Also, preservatives were not required to be added to the compositions according to examples No. 1, 2, 3, 10, 11, 12, 19, 20, 21, since the wastes of the extraction of non-metallic minerals and / or their enrichment waste containing layered silicates themselves have the properties preservatives. Unlike the composition according to example No. 28, they do not have a powerful irritating effect on the skin, and unlike the composition according to example No. 29, they do not have a weak irritating effect on the skin. Unlike both formulations, they cannot cause allergies.

Studies of the detergent properties of hair washing agents according to the compositions indicated in examples No. 4, 5, 6, 13, 14, 15, 22, 23, 24, as well as 30 and 31, were carried out according to the following scheme.

Three women with short haircuts and three types of hair were selected: oily, normal and dry, the hair was thoroughly washed and dried, sunflower oil 0.5 g was applied to the clean dried hair. After that, the hair was washed.

After drying with a hair dryer, the tactile sensation of the quality of cleanliness of the hair was assessed by the subjects themselves, on a five-point scale. The test subjects were not aware of the ingredients contained in this product to avoid subjective assessments.

As can be seen from our experiment, the product containing mineral processing products (example No. 4) removed excess fat well, along with the products prepared according to examples No. 30 and 31, while there was a feeling of clean hair. All detergents containing mining and / or enrichment wastes containing layered silicates gave the hair additional plumpness and ease of combing properties. The fat was removed from the hair so efficiently that it was required to additionally rinse it with a special agent to make the hair shine.

In examples No. 4, 5, 6, 13, 14, 15, 22, 23, 24, 30 and 31, all the compositions showed the same washing ability, which suggests that it is possible to wash hair in the waste of non-metallic minerals and waste their enrichment, containing layered silicates, to introduce or not to introduce additional substances, they qualitatively remove contaminants, both with them and without them. But also in the compositions according to examples No. 4, 5, 6, 13, 14, 15, 22, 23, 24, it was not required to add preservatives, since the wastes of the extraction of non-metallic minerals and their enrichment waste containing layered silicates themselves have the properties preservatives. And, unlike the composition according to example No. 30, they do not have a powerful irritating effect on the scalp, and unlike the composition according to example No. 31, they do not have a weak irritating effect on the skin. And unlike both formulations according to examples No. 30 and 31, they cannot cause allergies.

Experiments to study the washing properties for skin care and cosmetic removal indicated in examples No. 7, 8, 9, 16, 17, 18, 25, 26, 27, 32 and 33 were carried out according to the following scheme.

Three women were selected with three types of skin: oily, combination and dry, the face was washed and dried, sunflower oil 0.5 g was applied to clean dried skin with hands. After that, the skin was cleaned.

After drying with a hair dryer for 3 minutes, at a distance of 30 cm, the tactile sensation of the quality of skin cleanliness was assessed by the subjects themselves, on a five-point scale. The test subjects were not aware of the ingredients that the product contained in order to avoid subjective judgments.

The tool containing waste products from the extraction of non-metallic minerals (for examples No. 7, 8, 9, 16, 17, 18, 25, 26, 27, 32 and 33) removed excess fat efficiently, and did not give dry skin an unnecessary feeling of dryness.

In examples No. 7, 8, 9, 16, 17, 18, 25, 26, 27, 32, 33, all the compositions showed the same detergency, which suggests that for the preparation of a skin care product and the removal of cosmetics, you can waste from the extraction of non-metallic minerals and waste of their enrichment, containing layered silicates, to introduce or not to introduce additional substances, they qualitatively remove pollution both with and without them. But also in the compositions according to examples No. 7, 8, 9, 16, 17, 18, 25, 26, 27 it was not required to add preservatives, since the wastes of the extraction of non-metallic minerals and their processing waste containing layered silicates themselves have the properties preservatives. And, unlike the composition according to example No. 32, they do not have a powerful irritating effect on the skin of the face, and unlike the composition according to example No. 33, they do not have a weak irritating effect on the skin. And unlike both formulations, they cannot cause allergies.

Claims (1)

The use of wastes from the extraction and / or enrichment of non-metallic minerals containing layered silicates, bentonite, and / or saponite as components of a detergent.