WO1992016607A1

WO1992016607A1 - Demulsifying cleaning agent

Info

Publication number: WO1992016607A1
Application number: PCT/EP1992/000373
Authority: WO
Inventors: Reinhold HÖLLE
Original assignee: Alfred Kärcher GmbH & Co.
Priority date: 1991-03-12
Filing date: 1992-02-21
Publication date: 1992-10-01
Also published as: EP0575355A1; DK0575355T4; DK0575355T3; ES2076753T3; GR3030009T3; GR3017809T3; EP0575355B2; FI933986A; NO933246D0; FI933986A0; EP0575355B1; ES2076753T5; NO933246L; DE59203692D1; NO305523B1; FI109916B; ATE127831T1

Abstract

A demulsifying cleaning agent which can be used over a wide range of temperatures and which removes oils, fats and mineral impurities contains one or more nonionic tensides (NT) with a mean total HLB value (HLBG) greater than 12.0 to approximately 13.5 and one or more anionic tensides (AT) from the series of aliphatic or aromatic sulphonates. The nonionic tenside (NT) and the anionic tenside (AT) are present in a weight ratio V, where V = parts by weight NT/parts by weight AT (free acid form), which lies between approximately 2.9 and 16 if salts of aliphatic sulphonic acids are used and between 3.5 and 12.5 if salts of aromatic sulphonic acids are used.

Description

DESCRIPTION

Demulsifying detergent

The invention relates to a demulsifying cleaning agent which is particularly suitable for removing oil and grease contamination.

The area of use of such demulsifying cleaning agents is in particular the area of vehicle washing systems, such as Car wash systems or train cleaning systems are provided, in which high-pressure cleaning devices are often used.

The cleaning agents used hitherto, which are used to clean painted and unpainted surfaces of vehicles, engines, floors, facades, aircraft, etc., remove the oil and fat-containing contaminants by emulsifying from the surface and transfer the oil and fat components and the contaminant particles contained therein into the transport medium water. The focus of these cleaning agents is only on the complete removal of dirt. Due to the stable emulsification of the oil and fat components, but also the at least partial dispersion of the solid particles, a separation of these contaminants from the waste water in the cleaning system is not possible or only with great effort.

EP-A 213 554 also discloses a demulsifying cleaning agent with a surface moisturizing effect, the composition of which is particularly suitable for the absorption of fats and oils and for cleaning vertical surfaces, the so-called surface moisturizing effect being achieved by the special formulation of the cleaning agent becomes.

After a certain period of time, this cleaning agent separates the oil and fat components of the impurities through the demulsifying effect, so that these components can be separated from the dirty water phase. However, the cleaning effect of these cleaning agents is overall unsatisfactory, especially with regard to the removal of mineral soiling, e.g. Dusts, pollen etc.

It is the object of the invention to propose a demulsifying cleaning agent which, in a wide temperature range, removes oil and grease as well as mineral contaminants from the objects to be cleaned in a satisfactory form and which in particular also removes all types of hydrocarbons emulsified in the cleaning phase when the Waste water separates immediately as a separate phase.

The cleaning agent of the present invention should also be particularly suitable for use in high-pressure cleaning devices and brush washing systems. The separation effect in the wastewater should in particular also meet the new requirements for the wastewater to be discharged into the public sewer network, as specified, for example, in Appendix 49 of the General Framework Administrative Regulation on Minimum Requirements for the Discharge of Wastewater into Waters of December 19, 1989 is.

The above object is achieved with the cleaning agent described in the introduction in that the cleaning agent

comprises one or more nonionic surfactants (NT) with an average total HB value (HLB _G ) of> 12.0 to approximately 13.5 and furthermore one or more anionic surfactants (AT) from the series of aliphatic or aromatic Contains sulfonates; wherein the nonionic surfactants (NT) and the anionic surfactants (AT) are present in a weight ratio V, which is _{v =} parts by weight NT _, .__. _{h +} .

Parts by weight AT (free acid form) ^{9 D} 'and in the case of the use of aliphatic sulfonic acid salts in the range from about 2.9 to 16 and in the case of the use of aromatic sulfonic acid salts in the range from 3.5 to 12.5.

Cleaning agents of this type are ideally suited to cleaning oil and fat-containing contaminations, which in particular also contain mineral contaminants, such as dusts, pollen, etc., in a wide temperature range of approx. 15 to 70 ° C. The hydrocarbons, fats and oils of any kind emulsified during the cleaning process become instantly separated from the wastewater at rest, and so completely that the separable demulsified wastewater fully complies with the latest wastewater regulations.

The cleaning agents according to the invention achieve a very good cleaning effect with economical use of cleaning agents.

An essential advantage of the cleaning agent according to the invention is that the demulsifying properties are not lost even over the large temperature range of 15 to 70 ° C., which is not guaranteed with conventional cleaning agents of this type. 15 ° C is usually the water temperature that the cold water from the public water supply has. The temperature of 70 ° C is usually not exceeded when a hot water high pressure jet impacts a cleaning object.

Although the cleaning agent according to the invention can be used universally for all possible types of dirt, in particular also for mixed soiling from oil and fat as well as mineral soiling, the demulsifying effect is not lost. The central feature here is the mixing ratio of the nonionic surfactants, which is expressed by the HLBg value.

The ratio of anionic and non-ionic surfactants is also critical, since incorrect mixing here can also disrupt the demulsifying effect.

The cleaning agents according to the invention can be present both in solid form and in liquid form. The cleaning agent according to the invention can be formulated as a concentrate or as an agent prepared with water. In order to obtain a clear solution in the case of the liquid, water-containing cleaning agents, depending on the solubility of the individual components in water, a solubilizer is added in an amount of about 0.5 to 18% by weight.

A particular advantage of the present detergent mixtures is that they can be manufactured without phosphate.

Extensive tests have shown that alkylbenzenesulfonates are preferred as the anionic surfactant, so that preferred cleaning agents predominantly contain those as anionic surfactants, the weight ratio V between nonionic and anionic surfactants in this case preferably being 3.5 to 12.5 .

As an alternative to this, dialkyl sulfonate succinates have also proven themselves as anionic surfactants, and in the event that these anionic surfactants are predominantly present in the cleaning agent, a weight ratio V of approximately 2.9 to 11 is selected.

Another alternative for the anionic surfactants is the alkylnaphthalenesulfonates, in which case the weight ratio V is then set to about 3.5 to 12.

Another group of substances with which very good cleaning effects are achieved are the alkyl sulfonates, and in this case the weight ratio V will preferably be about 4 to 16.

In the case of the alkylbenzenesulfonates, the salts of sodium and ammonium and of triethanolamine are preferred. It was also found that the demulsifying effect of the cleaning agents according to the invention is somewhat concentration-dependent and, surprisingly, the concentration with which the best demulsifying effect is obtained coincides with the concentration range which results as the minimum surfactant concentration range.

This ensures economical use of detergents and a good cleaning action in a wide temperature range with the best possible demulsifying effect in wastewater treatment.

The nonionic surfactants are preferably selected from the group of C 1 -C 8 oxo alcohols, which alone or in a mixture with C 1 to

can provide the total nonionic surfactant content.

However, it is also possible to use Cg to C- _j fatty alcohol compounds alone as nonionic surfactants.

Owing to the relatively high proportion of nonionic surfactants in the cleaning agent according to the invention, these can be processed very well using cold and hot water high-pressure devices without the operation of the device being impaired by noticeable incrustations in the temperature range above 60 ° C. Depending on the hardness of the water available, it is recommended to provide a proportion of complexing agents in the cleaning agent in order to complex the existing water hardness. These complexing agents or builders are usually contained in the cleaning agent in a proportion of 0.5 to 25% by weight.

Corrosion inhibitors for light and colored metals are added. The proportion by weight of these substances is frequently between 0.1 and 25% by weight of the cleaning agent.

In addition, colorants and fragrances are usually added to the cleaning agent, but they play a minor role in terms of their weight percentage. The latter are usually between 0.0005 and 0.4% by weight.

It should be noted at this point that additives such as e.g. Complexing agents, corrosion inhibitors, dyes and fragrances for the cleaning agent according to the invention do not change its basic structure and characteristics, but that only additional, already known side effects are used here.

In particular, nothing changes in the excellent demulsification behavior over a wide temperature range and in the excellent cleaning action both for oil and fat-containing soiling and for soiling which is heavily permeated with street dust pollen etc.

The complexing agents are usually selected from the group EDTA, NTA, phosphonic acids and their soluble salts. The substances can be used individually or as a mixture.

If the cleaning agent according to the invention is used as a solid agent, so-called fillers are often added, which can make up between 10 and 80% by weight of the cleaning agent.

Suitable fillers are soda, borax, sulfates and urea. In order to meet special requirements, the cleaning agent can also have an alkaline content added, which can be, for example, up to 9% by weight of NaOH.

For cleaning applications with a different approach, it may be advisable to give the cleaning agent an acidic pH, and in this case an inorganic or organic acid is added, which can make up to 25% by weight of the cleaning agent.

If a clear liquid is to be obtained as a cleaning agent, solubilizers are used, as described above. The group of cumene sulfonates and their salts has proven to be favorable.

At this point it should be pointed out that the cumene sulfonate cannot be counted among the anionic surfactants in the form of aromatic sulfonates, since the cumene sulfonate has no surfactant effect.

The following are some examples of preferred formulations for detergents with a demulsifying effect, formulations 1, 3 and 4 relating to liquid detergents and formulation 2 a solid detergent.

All percentages are percentages by weight.

R e z e p t u r 1:

2% triethanolamine salt of alkylbenzenesulfonic acid

Alkyl radical = approx. C- ^ 8% C ₁₃ _ ₁₅ -0xo alcohol + 7 EO; HLB = approx. 12 8% C ₁₀ oxo alcohol + 7 EO; HLB = approx. 13 5% nitrilotriacetate trisodium salt 40% solution

3% sodium cumene sulfonate 40% solution

0.5% dyes, fragrances, preservatives 73.5% dem. water

R e z e p t u r 2:

2.6% C ₁₂ _ ₁ fatty alcohol + 8 EO; 90% HLB = approx. 13

2.8% C _{1] L} -0xoalcohol + 7 EO; 90%

1.0% Na salt of alkylbenzenesulfonic acid 92% powder

22.5% NTA nitrilotriacetate trisodium salt 92% powder

35.0% soda ash

25.0% Na metasiiikat ^* 5H ₂ 0

5.5% urea

4.0% heavy sodium sulfate

1.5% sodium cumene sulfonate powder

0.1% dyes / fragrances

R e z e p t u r 3:

2.5% Na dioctyl sulfosuccinate; 60% solution

1.5% Cin.ic alkyl sulfonate Na salt; 65% solution

10.0% C ₁₀ -xoalcohol + 7 EO; HLB = approx. 13

11.5% NTA nitrilotriacetate trisodium salt 40% solution

3.0% Na cumene sulfonate 40% solution

0.2% fragrances, dyes, preservatives

71.3% of that. Water. Recipe 4:

8.5% C _{1; L} -oxo alcohol + 7 EO; 90% solution

2.0% triethanolamine salt of alkylbenzenesulfonic acid

Alkyl radical = C ₁₂

3.0 »% aminotrimethylenephosphonic acid (ATMP); 50% solution

2.4% NaOH 50% solution

1.5% Na cumene sulfonate; 40% solution 82.6% dem. Water.

The formulation 5 named below again relates to a liquid cleaning agent and this cleaning agent was compared with the cleaning effect of a comparison formulation which is a conventional, highly effective car shampoo according to the prior art.

R e z e p t u r 5:

2.65% alkylbenzenesulfonate, alkyl radical = approx. C-, _2nd

5.00% C ₁₀ oxo alcohol + 11 EO

5.00% C ₁₃ _ ₁₅ -xoalcohol + 8 EO

25.00% nitrilotriacetate trisodium salt 40% solution

18.00% sodium cumene sulfonate; 40% solution

44.35% of that. water

Comparison recipe:

5.00% alkylphenol ethoxylate alkyl radical = approx. Cg EO degree = approx. 6 15.00% sodium cumene sulfonate 15.00% ether sulfate sodium salt R-0- (CH ₂ -CH ₂ -0) ₂ S0 ₃

1.00% NaOH 4.00% the water Test dirt with the following composition was used in the tests:

90.0% by weight spindle oil 5.0% by weight activated carbon 5.0% by weight quartz sand (fine)

Cleaning effect:

The cleaning agent according to recipe 5 and according to the comparison recipe were examined for their cleaning effect as a function of the cleaning time. The concentration of the cleaning agent was varied between 0.5% and 50%. The results are shown in the table below.

The number of times is defined as the ratio of the cleaning time of the recipe 5 required for complete degreasing to the time required to achieve complete degreasing with the comparison recipe.

When comparing the cleaning agent concentrations used, it is clear that in the range from about 0.5 to 5% by weight of the cleaning agent according to recipe 5, the best, i.e. the fastest, cleaning process is achieved. Furthermore, the demulsifying effect was investigated in a wide concentration range for recipe 5.

The percentages each relate to percent of the cleaning agent according to recipe 5 or the comparison temperature in water. Table:

Test results on the cleaning effect

Time Z comparison recipe

1 1 1 1 1

1

z = required cleaning time recipe 5 *)

Required cleaning time, comparison recipe *)

*) Based on the complete degreasing

Demulsification:

In test tubes (200 ml long, 15 mm in diameter) 50 ml detergent solution (recipe 5) in concentrations of 5%, 3%, 2%, 1%, 0.5%, 0.25%, 0.1% and 0.05% and 0.2 g of red-colored spindle oil were added.

This mixture was stirred with a spatula stirrer (80 x 15 x 1.5 mm) at an immersion depth of 80 mm at a speed of 2,000 revolutions / minute for two minutes. After the stirrer was immediately removed, the solutions were left to stand for 5 minutes. Then 2 ml of sample was taken at half the liquid level and the extinction of the red-colored oil still present was measured with a spectral line photometer at a wavelength of 535 nm. The oil dye Sudan Red 403 liquid absorbs very well at this wavelength and is contained in the spindle oil with 0.05%. Measured values:

5.0% solution: extinction = 0.032

3.0% solution: extinction = 0.031

2.0% solution: extinction = 0.018

1.0% solution: extinction = 0.010

0.5% solution: extinction = 0.007

0.25% solution: extinction = 0.012

0.1% solution: extinction = 0.041

0.05% solution: extinction = 0.118

Each value is the average of three measured values.

This experimental arrangement shows very clearly that the demulsifying behavior depends on the application concentration of the cleaning agent.

The optimal application concentration of recipe 5 is 0.5%, but it can also be processed with acceptable demulsifying properties in the range of 0.25 - 2.5%.

The test test in section "Cleaning Effect" proves that a good cleaning result is still achieved with 0.5% application.

The same test arrangement was repeated with 2%, 1% and 0.5% detergent solution according to recipe 5, with 15 and 25 ml carefully removed from the test tube (below) and, after preparation as described in DIN 38 409 H18, with the Horiba OCMA 220 oil analyzer. The converted residual hydrocarbon content of the extracted solutions was less than 20 ppm. (20 mg / 1).

The principle of operation of the oil analyzer is based on the DIN regulation DIN 38 409 H18. Incrustation behavior:

In test tubes (200 ml long, 15 mm in diameter), 70 ml detergent solution (recipe 5 in demineralized water) in concentrations of 5%, 4%, 3%, 2%, 1%, 0.5%, and 0.25 % and heated in a saturated water vapor atmosphere in an autoclave to 135 ° C. at an operating pressure of 3-4 bar for 15 minutes.

These test conditions correspond approximately to those in a conventional hot water high-pressure cleaning device.

After cooling to room temperature, the detergent solution was removed from the test tubes and the residues / deposits on the glass walls were assessed visually.

Up to the 4% concentration, no deposits were found on the glass walls at the 5% concentration.

Claims

Expectations

1. Demulsifying cleaning agent, in particular for removing oil and grease contaminants containing inorganic contaminants

one or more nonionic surfactants (NT) with an average total HLB value (HLB _G ) of> 12.0 to approximately 13.5 and one or more anionic surfactants (AT) from the series of aliphatic or aromatic sulfonates; the nonionic surfactants (NT) and the anionic surfactants (AT) being present in a weight ratio V which is known as

Parts by weight of NT.

^{Parts by} weight AT (free acid form) ^rg 'and in the case of using aliphatic sulfonic acid ^salts in the range from about 2.9 to 16 and in the case of using aromatic sulfonic acid salts in the range from 3.5 to 12.5.

2. Cleaning agent according to claim 1, characterized in that it comprises a solubilizer in an amount of about 0.5 to 18 wt.%, And optionally a complexing agent in a concentration of at least 0.5%.

3. Cleaning agent according to claim 1 or 2, characterized in that the cleaning agent is phosphate-free.

4. Cleaning agent according to claim 1 to 3, characterized in that alkylbenzenesulfonates are predominantly present as the anionic surfactant and that the weight ratio V is approximately 3.8 to approximately 12.5.

5. Cleaning agent according to claim 1 to 3, characterized in that predominantly dialkyl sulfonate succinates are present as the anionic surfactant and that the weight ratio V is approximately 2.9 to approximately 11.

6. Cleaning agent according to one of claims 1 to 3, characterized in that predominantly alkyl naphthalene sulfonates are present as an anionic surfactant and that the weight ratio V is approximately 3.5 to approximately 12.

7. Cleaning agent according to one of claims 1 to 3, characterized in that alkyl sulfonates are present as the anionic surfactant and that the weight ratio V is about 4 to about 16.

8. Cleaning agent according to one of claims 1 to 7, characterized in that the alkyl groups of the aliphatic and aromatic sulfonates

Ciss_i4 alkyl groups include.

9. Cleaning agent according to one of claims 1 to 8, characterized in that C ι ₅ fatty alcohol compounds are contained as nonionic surfactants.

10. Cleaning agent according to claim 9, characterized in that the fatty alcohol compounds are oxo alcohol compounds.

11. Cleaning agent according to claim 10, characterized in that the oxo alcohol compounds include C ₁₃ _ ₁ c-oxo alcohols.

12. Cleaning agent according to one of claims 1 to 11, characterized in that the sulfonic acid salts are alkali metal salts, in particular sodium salts, ammonium salts or alkanolamine salts.