DE1091263B - Process for the production of cleaning agents with a low bulk weight - Google Patents

Description

The present invention relates to a method for the production of flaky, free-flowing while of storing non-caking detergents containing anionic synthetic detergent raw materials of low bulk density.

In the production of powder detergents and dishwashing detergents, efforts are increasingly being made to avoid dusty, to manufacture granular products. The production of these cleaning agents, the synthetic, contain surface-active, in particular anion-active organic compounds, by various methods.

The so-called Tennen process is only used to a very limited extent, which is very laborious and leads to products with a high bulk density.

The known spray processes, namely the cold and above all the hot spray process, are of greater importance. After that, the ones required for the construction of the respective detergent or dishwashing detergent were used Ingredients and water a sprayable, generally 40 to 60% solids and 60 to 40% water containing slurry which was dried in a spray dryer. Cold or hot spray powders were obtained depending on the atomization temperature.

With cold atomization, the pulp was converted into powder by atomizing and dissipating cold air convicted. A crystallization process essentially takes place, with the water content of the Approach is only slightly reduced. The cold spray powders have the disadvantage that they have a very small grain size accumulate, are difficult to dose and develop an unpleasant dust.

Coarse-grained and therefore easier to dose washing powders were the preferred ones after the one used today Obtained hot spray process, in which small hollow spheres of low bulk density are formed. The hot spray process however, has a number of disadvantages. The creation of the extensive system requires a high capital outlay, so that the process is only economical if the plant is continuous Day and night shifts are operated. The grain size of the hollow spheres obtained varies within one wide area. In order to obtain a detergent or dishwashing detergent with a grain size that is as uniform as possible, must therefore a relatively high return must be accepted. The amount of dust that is added to the pulp in the Circuit must be fed back, can be up to 30% of the spray product obtained. To this Way, not only the throughput is reduced, but also through the multiple necessary evaporation of water operating costs are also increased.

The present invention avoids these disadvantages and allows the production of detergents from low bulk density using gasent manufacturing processes

of detergents
of low bulk density

Applicant:

Colgate-Palmolive Company,
New York, NY (V. St. A.)

Representative: Dr.-Ing. G. Knoth, patent attorney,
Hamburg-Wellingsbüttel, Up de Worth. 24

Dr. Lojo Habicht, Aumühle (Hamburg district),

Dr. Arno Kluge, Hamburg-Fuhlsbüttel,

Glenn Ashmore Glossop, Short Hills, N.J. (V. St. A.), and Per Hjorth Rasmussen, Copenhagen,

have been named as inventors

wrapping fabrics. It is characterized by the fact that a water-containing paste is produced from the components required to build up the detergent or rinsing agent, as well as compounds that react in the heat to form gas, preferably carbon dioxide, and form this into thin strips, such as ribbons, it is dried by means of hot gases and finally broken down mechanically into particles of the desired size. The deformation of the paste can be carried out on a Pilier roller mill. The drying is expediently carried out by means of hot gases, such as hot air, at a temperature of 100 to 250 ^° C., preferably in countercurrent. According to a particular embodiment of the invention, sodium carbonate or sodium bicarbonate and acidic salts, such as disodium pyrophosphate, or acids, such as boric acid, are added to the paste and / or the slurry. Sodium bicarbonate and alkaline earth salts, preferably alkaline earth carbonates or magnesium sulfate, can also be incorporated into the slurry or paste. According to a further embodiment, sodium bicarbonate alone is added to the slurry or paste in the absence of alkali metal phosphates and alkali metal silicates.

The process according to the invention is simple and therefore economical In a way, flaky detergents and dishwashing detergents with a low bulk density between 0.35 and 0.45 are obtained,

009 628/396

the proportion of dust being so small that it is not necessary to return it.

The production of shaped washing raw materials in flake form by drying on rollers is known. However, considerable difficulties arise in this case, which only occur in the case of alkylarylsulfonate pastes with a low content Sodium sulfate can be overcome. Therefore, such flakes have a high content of detergent Fabric that fluctuates between 80 and 85% depending on the moisture content. The production of Detergents in flake form because they are practically salt-free, highly concentrated synthetic pastes with high purchase costs must be used (St up el, "Synthetic detergents and cleaning agents", Stuttgart, 1954, P. 291). The use of such high-percentage detergents with over 70% detergent substances without a structural substance also contradicts experience with the optimal composition of such substances Products because the synthetic detergent raw materials achieve their optimum effectiveness in low concentrations and their properties are better promoted by adding washing alkalis than by increasing the concentration of active washing substance.

According to the present invention, on the other hand, it is possible to produce flaky elements which are particularly suitable for practical use Winning detergents and dishwashing detergents whose content of active washing substance is significantly below 70% and which can be between 20 and 40%.

According to the new method, the necessary for the construction of the detergent or dishwashing detergent will be used organic and inorganic constituents, including those for the development of the inert gas, preferably of carbon dioxide, required propellant in a mixer first made a paste, which then by a suitable device, preferably by rolling, e.g. B. on a soap piling machine, too thin, endless webs, such as ribbons, are deformed and then dried. By rolling the paste if an intimate mixing and a homogeneous distribution of the gas-evolving fuels is achieved, see above that during drying a uniform development of the propellant gas and thus a uniform expansion of the Dry goods is achieved. The dry product has a fine-pored structure and is easy to shred. Preferably the drying is carried out by hot gases, such as

Na ₂ CO ₃ + Na ₂ H ₂ P ₂ O ₇
2NaHCO ₃ + Na ₂ H ₂ P ₂ O ₇

Air from about 100 to 250 ⁰ C, for example on a belt or turbine dryer performed. It can also be carried out by means of exhaust gases or in a vacuum or by infrared radiation. The porous dry material can easily be brought into the desired flake size by letting it pass through a wide-meshed sieve.

It is known that detergent granules can be inflated by drying bicarbonate-containing detergent pastes by shaping the paste into small granules and briefly exposing them to ^{a radiation source of about 1000 ° C. in a thin layer.} In this case, although inflation can be achieved, the process is cumbersome and uneconomical, and the washing-active substances are adversely affected by the heat shock.

It has been found that it is useful to include such inorganic compounds in the detergent paste incorporate an inert gas, preferably at the low drying temperature Carbon dioxide are able to evolve, while the carbon dioxide evolves according to the known process achieved by thermal decomposition of the added bicarbonates at very high temperatures became.

The most suitable has been found to be the addition of such inorganic compounds that are mutually under Carbon dioxide development react or form unstable, carbon dioxide-releasing compounds. Even Nitrosocarbonyl compounds, such as nitrosourea or nitrosourethane, which in the heat in carbon dioxide and Nitrogen disintegrate, or dicarboxylic acid salts of nitrosoalkylamide, such as N, N'-Dinitroso-N, N'-dimethylterephthalamide, which only supplies nitrogen as propellant gas when decomposed, and similar compounds can be used as Propellants are used.

The evolution of carbon dioxide can take place in various ways. Fuels for which the Carbon dioxide development already occurs when the ingredients are mixed with the detergent or detergent paste normal temperature sets in, as with mixtures of sodium carbonate or sodium bicarbonate and Sodium bisulfate. On the other hand, a weakly acidic and highly suitable additive is disodium pyrophosphate. the according to the equation

- »Na ₄ P ₂ O ₇ + CO ₂ + H ₂ O
- »Na ₄ P ₂ O ₇ + 2CO ₂ + H ₂ O

ongoing reactions lead to the formation of 50. CO _{2 can} develop in the detergent paste

Sodium pyrophosphate, the presence of which in washing also has with good success the reaction of boric acid with

detergents are desirable, but soda is not necessarily used in dishwashing detergents, according to the following equation

is required. runs:

2H ₃ BO ₃ 2HBO ₂ + Na ₂ CO ₃ by sodium bicarbonate

100 ⁰ C 2HBO ₂ + 2H ₂ O
2NaBO ₂ + CO ₂ + H ₂ O

A substitute for the soda
not possible because the CO ₂ development is then already carbonate, or magnesium carbonate or water-soluble alkaline earth sulfates, such as magnesium sulfate, on the one hand and

starts when mixing. 60 sodium bicarbonate on the other hand to the detergent paste.

Another possibility for CO ₂ development is that these compounds only react with one another above

50 ⁰ C with formation of alkaline earth bicarbonate, which then breaks down into carbon dioxide and alkaline earth carbonate:

has proven to be particularly suitable, consists in the addition of alkaline earth carbonates, preferably calcium

2NaHCO ₃ + CaCO ₃
Ca (HCO ₃ ),

2NaHCO ₃ + MgSO ₄
Mg (HCO ₃ ),

> 50 ° C

> 50 ° C Ca (HCO ₃ I ₂ + Na ₂ CO ₃
CaCO ₃ + CO ₂ + H ₂ O

Mg (HCO ₃ ), + Na ₂ SO ₄
MgCO ₃ + CO ₂ + H ₂ O

5 6

The magnesium sulphate can be used both as water of crystallization.

Magnesium sulphate containing (MgSO ₄ -7 H ₂ O) as well as in medium are generally used in equimolecular form, corresponding to the dehydrated form, advantageously as kieserite (MgSO · H ₂ O), guided reaction equations. Quantities applied, however, excesses are not

The method of equation (a) above is harmful. The addition of alkali carbonate, alkaline earth especially good for the production of detergents and the carbonate or alkali bicarbonate is expediently about according to (b) suitable for the production of detergents. 3 to 17%, preferably 3 to 10%, of the disodium

A considerable advantage of the pyrophosphate according to the invention 20 to 23%, the boric acid about 6 to Driving is the possibility of the water content to a 12% and that of magnesium sulfate monohydrate approximately To be able to set a certain value, which is expediently from 6 to 16%, preferably from 8 to 10%, to the anhydrous up to about 10%, preferably 5 to 8%, calculated without detergents or dishwashing detergents.

As alkali carbonate can be potassium or sodium carbonate

is pregnant. be used. Of the alkaline earth carbonates are

It has also been found that detergents of low bulk density, preferably calcium or magnesium carbonate, are obtained if the detergent uses the calcium carbonate as natural chalk or as paste only sodium bicarbonate is added, since precipitated calcium carbonate, the magnesium carbonate in the decomposition pressure of the Sodium bicarbonate in commercial form as extra light, medium light temperatures above 100 ⁰ C is higher than 760 mm Hg. or heavy carbonate. Magnesium sulfate is preferred- The sodium bicarbonate additive is only suitable as a monohydrate, e.g. B. in the form of the natural production of detergents that contain no phosphates and ao kieserite, to reduce the water content of the silicates. The bulk density of phosphate and drying paste should be kept as low as possible

Sodium bicarbonate practically not lowered. essential addition. If the magnesium monohydrate in

The water content of the pastes according to the invention in amounts below 6%, added or omitted entirely, is generally only about 15 to 25% and is thus the detergent pastes are not or only with difficulty significantly less than the water content of the bar.
Hot spray drying required approaches. The paste can be used in the manufacture of dishwashing detergents

It was very surprising that the invention also advantageously had 1 to 2% potassium stearate soap in the form Pastes composed according to the formula can be added to a 10 to 15% solution. the Let the soap piling machine mushroom well, which does not act as a scaffolding. she The case is when the detergent or dishwashing detergent pastes none envelops all of the ingredients and prevents a too fast the carbon dioxide-evolving escape of the carbon units developed during drying according to the invention because they are sticky then and from dioxyds.

Rollers are not promoted. As a result of the mushrooming, water-based,

In a simple way, a completely homogeneous paste-like detergent raw materials have been shown, such as the sodium salts Mixing of the constituents is achieved, and at the same time, polypropylene benzenesulfonates with 9 to 18, preferably endless, thin ribbons with a large surface are preserved, with 12 to 15 carbon atoms in the polypropylene chain which are continuously fed to the drying device and the sodium salts of alkyl sulfuric acid esters will. of such higher molecular weight fatty alcohols, which are

After cooling with cold air, the 40 can be produced from fatty acid mixtures from tallow or coconut oil Product after drying lightly on a sieve, are made.

advantageously of 16 meshes / cm ² , with the addition of these washing raw materials can be added to the pastes

Detergent or washing-up liquid accumulates in flakes. Since the foam effect or detergency-improving additives, dried product prior to sieving, such as fatty acid alkanolamides, e.g. B. Coconut fatty acid monopowder So parts are not present, occurs with 45 ethanolamide, or ethoxylated fatty acid alkanolamides, Practically no dust sieving. can be added. Both sodium

The drying of the piliorten intermediate product can be tripolyphosphate, sodium pyraphosphate, sodium pljos through Infrared, vacuum? or hot air drying, phate or mixtures of these phosphates are used, follow, the latter being the most economical. Sodium sulfate or others can also be used in the paste

Especially when using exhaust gases and, in turn, washing alkalis and the washing process improving stream using a belt or turbine additives, such as carboxymethyl cellulose, advantageously as a dryer at a temperature that is advantageously about 33% powder, sodium silicate, optical brighteners and 150 up to 200 ° C. Be present without the addition of the CO _a -developing dyes.

Propellant is a 50% longer drying time. The silicates are preferably in powder form in the

necessary; and the dry material becomes so firm that it is incorporated into the paste to reduce the water content of the paste difficult to push through a sieve. At the same time, keep it as low as possible. So can di- or trisilicates the bulk density increases to over 0.6. The layer thickness used in the form of commercially available water glass the piled material can be pre-prepared during the drying process.

Ganges with looser, a good stroke of the After the method according to the invention can also

Up to several 60 detergents containing perborate can be produced to ensure dry air storage, if Be centimeters. The drying can also be promoted by disodium pyro-promoting additives which develop as carbon dioxide of the tape through the dryer in phosphate and sodium bicarbonate and as perborate continuous Operation. stabilizer magnesium silicate can be used. Such a

To ensure that the composite according to the inventiveness detergent contained by the track method according washing or detergent produced voltage 65 at 150 ⁰ C more than 90% of the originally present free-flowing, that are free-flowing and non-active oxygen during storage.

caking, their water content may be a certain The manufacture of detergents and dishwashing detergents according to the

Do not exceed the height. In the case of detergents according to the invention, it is determined by the following up to about 10%, preferably 5 to 8%. and illustrated with rinsing examples. All quantities are average up to about 0.5% x 7 ° amounts by weight.

7 8

In Examples 1 to 5, the pastes are used in the same Example 4

Way prepared by first putting the detergent with 20% alkylarylsulfonate and in a mixer

Detergent raw material paste and the other ingredients - 5 <y _o fatty alcohol sulfate (FAS)

parts expediently added in the following order _XT . ,,

are: fatty acid alkanolamide, optionally water, 5 sodium tetrapropylene benzene sulfonate paste

Soda water glass, carboxymethyl cellulose, sodium _XT ^. ^{/ o} ,, V "* '"*'';' V, ^ ' ^{5U ielle}

bicarbonate, magnesium sulfa monohydrate, phosphate and sodium coconut fatty alcohol sulfonate paste

finally sodium sulfate. After all components are good ^ '<> ** ^Α ^>: · ·' · · ·; ·· ·; ° - ° £ i ^e !} ^E

are mixed, the paste is piled, the piled good ^ T ^^^ ™ ^

dried and the dry material through a sieve of io carboxymethyl cellulose (33% CMC) 1 ^ ??

16 meshfcm * given sodium bicarbonate 7.00 parts

Magnesium sulfate monohydrate 7.95 parts

Example 1 Sodium Tripolyphosphate 35.00 parts

Detergent with 35% alkyl aryl sulfonate (AAS) water 5 00 parts

^{10 JJ v} 'water content of the paste 21.7%

Natriumtetrapropylenbenzolsulfonatpaste ¹⁵ hot-air drying at 190 ⁰ C

(54.6% AAS) 64.25 parts water content of the detergent 6%

Soda water glass (trisilicate) 7.05 parts bulk density of the detergent 0.45

Carboxymethyl cellulose (33% CMC) 1.50 parts

Sodium bicarbonate 7.00 parts Example 5

Magnesium sulfate monohydrate 8.65 parts ²⁰ detergent with 25% alkyl aryl sulfonate

Sodium tripolyphosphate 35.00 parts

The water content of the paste is 24.1%. The dry sodium tetrapropylene benzene sulfonate paste

drying is carried out with hot air at 200 ⁰ C. The detergent _T ⁽⁵² / o ^AAB). ····· ^{48 <15 parts}

contains 7.7% water and has a bulk density of coconut fatty acid monoethanolamide (30%) .. 6.65 parts

0.43. As the sieve sample listed below shows, ^a5 sodium sulfate 8.75 parts

the dust content of the detergent is very low. Soda water glass (Disihkat) 7.35 parts

^{8 5} Carboxymethyl Cellulose (33% CMC) 1.50 TeUe

Sieve sample of sodium bicarbonate 7.00 parts

Magnesium sulfate monohydrate 7.95 parts

On test sieves of the following mesh sizes, 30 sodium tripolyphosphate 35.00 parts remain

previous: sodium sulfate 10.40 parts

Mesh size 1.68 mm 0.6% Water content of the paste 23.0%

Mesh size 0.84 mm 46.9% hot air drying at 190 to 200 ^° C

Mesh size 0.43 mm 33.8% Water content of the detergent 6.0%

Mesh size 0.25 mm H, 9% 35 bulk density of the detergent 0.41

Mesh size 0.177 mm 3.5%

Mesh size 0.15 mm 0.9% Example 6

Through the sieve DIN 0.15 according to detergent containing perborate with 30%

According to DIN 1171 flow 2.4% alkyl aryl sulfonate

100.0% ⁴ ° The preparation of the paste and its further processing _R. -ίο t ^un g is carried out in the same way as in example 1 to 5.

P The components are in the order listed

Detergent added with 35% _{of the} alkyl aryl sulfonate detergent base paste.

,. . ! ,, ij-xi sodium tetrapropylene benzene sulfonate paste

Natnumtetrapropvlenbenzenesulfonatpaste ₄ r, _{A1 Qo /} δ αc \ ω _ςτ ·,

^{v 45} (61.8% AAS) 48.5 parts

(oil, yo _{; 0} AAb) ···. · - ■ · · ■ o ', like the carboxymethyl cellulose solution (3%) 16.6 tea

Soda water glass Disihkat 7.35 parts

Carboxymethyl cellulose (33% CMC) 1.50 parts ^^ ί-Ι ^^ ........ ! ..... lil S

Sodium bicarbonate 7.00 parts _XT , · ", ^""" u "" + 1 α q τ μ

,. . ,,, "ij, οVvn -τ- · ι sodium bicarbonate 16.0 Ieile

Magnesium sulfate monohydrate 8.00 _{parts 50 DinatriurapyrO phosphate 2} 2.2 parts

Sodium tripolyphosphate. ₃₅₀₀ parts of _sodium tn £ oly J _hoi £ _{has 6> 5} parts

S ^a m ^ei lf ί r ⁰ ethylenediaminetetraacetic acid sodium,

Hot air drying at. 200 ⁰ C 3 ^ _{Lösu 2Q} ^

Water content of the detergent 6.4% Water content of the paste 23 4 »/

Bulk density of the detergent .... 0.4 ₅₅ Hot air drying at . '.'. '.'. '.'. '.'. '.'. '.'. 150 ° C

Example 3 Water content of the detergent 6.5%

..., ...,., "_., .... , _{R A} bulk density of the W ^T aschmitteIs 0.40

W Detergents with 35 "/" alkylarylsulfonate _yet ^ _{orhandener active} oxygen,

Sodium tetrapropylene benzene sulfonate paste on the amount of perborate applied

(52% AAS) 67.30 parts 60 calculates 95%

Soda water glass (trisilicate) 7.05 parts The manufacture and processing of the detergent

Carboxymethyl cellulose (33% CMC) pastes containing 1.50 parts for detergents according to Examples 7 to 11

Sodium bicarbonate 7.00 parts is made in the same way as for detergents.

Magnesium sulfate monohydrate 8.00 parts The ingredients are preferably used in the specified

Sodium tripolyphosphate 17.50 parts 65 mixed order.

Sodium pyrophosphate 17.50 parts Rpi «™! 7th

Water content of the paste 25% ice cream. /

Hot air drying at 200 ° C detergent with 30% alkyl aryl sulfonate

Water content of the detergent 6.4% sodium tetrapropylene benzene sulfonate paste

Detergent bulk density .... 0.37 70 (52.9% AAS) 56.7 parts

Potassium stearate solution (10%) 6.6 parts

Methyl cellulose solution (10%) 4.4 parts

Boric acid 6.2 parts

Sodium carbonate 5.3 parts

Sodium sulfate 49.4 parts

Calcium carbonate (natural chalk) 7.0 parts

Water content of the paste 24.5%

Drying of the piled good

Infrared drying at 110 ^° C

Water content of the detergent 0.5%

Bulk density of the detergent 0.45

Example 8
Detergent with 25% alkyl aryl sulfonate

Sodium tetrapropylene benzene sulfonate paste

(54.6% AAS) 45.9 parts

Sodium bicarbonate 7.0 parts

Calcium carbonate (natural chalk) 4.2 parts

Sodium sulfate 63.7 parts

Water content of the paste 16%

Hot air drying at 200 ° C

Water content of the detergent 0%

Bulk density of the detergent 0.41

Example 9
Detergent with 23% alkyl aryl sulfonate

Sodium tetrapropylene benzene sulfonate paste

(52.9% AAS) 43.5 parts

Potassium stearate solution (10%) 10.0 parts

Water 3.3 parts

Sodium bicarbonate 7.0 parts

Calcium carbonate (natural chalk) 2.1 parts

Magnesium carbonate, medium-light 1.8 parts

Sodium sulfate 64.4 parts

Water content of the paste 23%

Infrared drying at 110 ° C

Water content of the detergent 0.2%

Bulk density of the detergent 0.38

Example 10
Detergent with 30% alkyl aryl sulfonate

Sodium tetrapropylene benzene sulfonate paste

(54.6% AAS) 55.00 parts

Sodium bicarbonate 7.0 parts

Magnesium carbonate 3.55 parts

Sodium sulfate 59.00 parts

Water content of the paste 18.6%

Hot air drying at 190 ^° C

Water content of the detergent 0.3%

Bulk density of the detergent 0.37

Sieve sample

The detergent according to Example 10 remains on test sieves of the following mesh sizes:

Mesh size 1.68 mm 0.25%

40

Mesh size 0.84 mm 21.20%

Mesh size 0.43 mm 30.20%

Mesh size 0.25 mm 29.60%

Mesh size 0.177 mm 11.00%

Mesh size 0.15 mm 2.35%

5.40% flow through the DIN 0.15 sieve

100.00%

Example 11
Detergent with 30% alkyl aryl sulfonate

Sodium tetrapropylene benzene sulfonate paste

(52% AAS) 57.8 parts

Sodium bicarbonate 5.0 parts

Sodium sulfate 64.6 parts

Rhodamine B solution (0.1%) 0.5 parts

Water content of the paste 20.6%

Hot air drying at 200 ^° C

Water content of the detergent 0.4%

Bulk density of the detergent 0.35

Claims (6)

Patent claims: 1. A process for the production of detergents of low bulk density using gas-evolving substances, characterized in that the components required to build up the detergent or rinsing agent and compounds which react in the heat with the formation of gas, preferably carbon dioxide, are a water-containing one Produces paste, shapes them into thin webs, such as ribbons, dries them, preferably by means of hot gases, and finally crushes them mechanically into particles of the desired size. 2. The method according to claim 1, characterized in that the deformation of the paste on a Pilierwalzwerk is made. 3. The method according to claim 1 or 2, characterized in that the drying by means of hot gases, such as hot air, at a temperature of 100 to 250 ° C, preferably in countercurrent. 4. The method according to claim 1 to 3, characterized in that the paste or sodium carbonate Sodium bicarbonate and acid salts such as disodium pyrophosphate or acids such as boric acid are added which only cause carbon dioxide to develop at elevated temperature. 5. The method according to claim 1 to 4, characterized in that the paste and sodium bicarbonate Alkaline earth salts, preferably alkaline earth carbonates or magnesium sulfate, are incorporated. 6. The method according to claim 1 to 5, characterized in that the paste alone is sodium bicarbonate is added in the absence of alkali phosphates or alkali silicates. © 009 628/396 VS.