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The performance builder for a bright future SKS®- 6

The performance builder for a bright future

SKS®- 6

The performance builder for a bright future SKS®- 6

SKS®-6

contentS

IntroDuctIon

4

PhySIcal anD chemIcal ProPertIeS

12

Manufacturing

6

Water softening properties

14

SKS-6 characterisation

7

Alkalinity and reserve alkalinity

18

Product range, particle structure and morphology

10

Dispersed particle size, solubility and dispersing properties

20

 

Storage properties

22

Water uptake

23

Surfactant uptake

24

Compatibility with other detergent ingredients

26

Precipitation and inorganic incrustations

28

Heavy metal binding capacity

31

envIronmental anD Safety aSPectS

32

Life cycle inventory

34

Solubility in waste water

35

Exposure modelling

37

Toxicology of SKS-6 and SKS-6 based detergent formulations

38

launDry DetergentS

40

aPPenDIx

60

Basic detergent effects

42

Glossary

62

Compact detergents

44

Patents

64

Laundry tablets

47

Abbreviations

65

Regular detergents

48

Literature

66

Color detergents

50

Product range

67

Fine-fabric detergents and water softeners

51

automatIc DIShwaShIng DetergentS

52

Automatic dishwashing detergents

54

Cleansing performance

56

Formation of deposits in the dishwasher

57

SKS-6

IntroDuctIon

SKS-6 – The performance builder for a bright future

Washing is something that is done throughout the world, on every continent. However, modern detergent formulations must also cater individually for a wide range of requirements in various countries to enable optimum results to be obtained. Particularly in the area of builders, detergent formulations have undergone a change in last decades.

5

For years, sodium tripolyphosphate was used as the universally preferred builder. Concerns about the possible eutrophication of rivers and lakes have led to a decline in the use of this builder, which differs from region to region.

The need to have an alternative to sodium tripolyphosphate initiated an intensive worldwide search for suitable substitutes. Combinations of zeolite A with polycarboxylate and soda ash were developed as a phosphate substitute. Although soluble and insoluble builders have been used for many years, so far no builder has been available whose advantages as a whole combine to meet the varied requirements of a modern builder.

Intensive research has resulted in the development of a certain type of layered sodium silicate. The SKS-6 type has proved to be the most promising one in terms of its positive properties for use in detergents.

The SKS-6 type has proved to be the most promising one in terms of its positive

SKS-6

manufacturIng

For the manufacture of SKS-6, sand and caustic soda are converted to water glass and this is then spray-dried (Fig. 1). This powdery amorphous sodium disilicate crystallises to layered silicate through special temperature control. Other process steps such as grinding and compacting lead to the individual commercial products.

and compacting lead to the individual commercial products. fIgure 1: Manufacturing of SKS-6 Sand Soda ash

fIgure 1: Manufacturing of SKS-6

Sand

Soda ash or caustic soda

water glass solution

Spray drying

amorphous disilicate

Crystallisation

SKS-6

Milling

SKS-6 powder

Compaction

SKS-6 granular

Compaction,

Agglomeration,

Additives

SKS-6 cogranular

SKS-6

characterISatIon

SKS-6 belongs to the chemical group of sodium disilicates with the molecular formula Na 2 Si 2 O 5 . These demonstrate the phenomenon of polymorphism, i.e. the ions can be linked together, with the same total composition in different space arrangements, different lattice structures. Four forms occur most frequently: alpha-, beta-, delta- and epsilon-sodium disilicate. Common to the structures is that silicon and oxygen ions unfold two-dimensional layers, in the form of linked tetrahedra. Sodium ions situated between the layers ensure charge equalisation.

fIgure 2: Crystal structures of sodium disilicate

alpha-sodium disilicate

structures of sodium disilicate alpha-sodium disilicate Beta-sodium disilicate Delta-sodium disilicate The different

Beta-sodium disilicate

disilicate alpha-sodium disilicate Beta-sodium disilicate Delta-sodium disilicate The different polymorphous phases

Delta-sodium disilicate

disilicate Beta-sodium disilicate Delta-sodium disilicate The different polymorphous phases differ essentially in the

The different polymorphous phases differ essentially in the angles in which the individual tetrahedra are arranged to one another (Fig. 2).

As a technical product, SKS-6 is composed mainly of the delta phase with small shares of the alpha and beta phases.

SKS-6, primarily the delta phase, can undergo some varying reactions in tap water. These are then the basis for the multifunc- tional application profile. First, water molecules that come into contact with SKS-6 on the solid’s surface are deprotonised. This leads to the formation of hydroxide ions in the solution and is the cause of the high alkalinity supply of SKS-6 (Fig. 3). At the same time, a sodium hydrogendisilicate, kanemite, is formed. As a result of the uptake of water of crystallisation in kanemite the layered silicate separates and the crystal framework expands. As this cannot be without an influence on the solubility and dispersing capability, a very rapid disintegration of the disilicate granules in the water is observed.

fIgure 3: Reactions of delta-sodium disilicate

Ion exchange with proton/Providing alkalinity

Na 2 Si 2 O 5 + 4 H 2 O

alkalinity Na 2 Si 2 O 5 + 4 H 2 O NaHSi 2 O 5  · 3 H

NaHSi 2 O 5  · 3 H 2 O + Na + + OH

Ion exchange with ca 2+ and mg 2+ (me 2+ )/ water softening

2 Na 2 Si 2 O 5 + Me 2+ 2 NaHSi 2 O 5  · 3 H 2 O + Me 2+

2 NaHSi 2 O 5  · 3 H 2 O + Me 2 + »Me (NaSi 2 O 5

»Me (NaSi 2 O 5 ) 2 «+ 2 Na +

»Me (HSi 2 O 5  · 3 H 2 O) 2 « + 2 Na + 2 O 5  · 3 H 2 O) 2 « + 2 Na +

hydrolysis/Providing water glass

>> 20 H 2 O

+ hydrolysis/Providing water glass >> 20 H 2 O Na 2 Si 2 O 5 + 2 OH

Na 2 Si 2 O 5 + 2 OH NaHSi 2 O 5  · 3 H 2 O + 3 OH

2 SiO 3 2- + H 2 O + 2 Na +

2 SiO 3 2 - + 5 H 2 O + Na + 3 2- + 5 H 2 O + Na +

Delta-sodium disilicate and kanemite can undergo an exchange with various cations. In particular these are the hardness-forming calcium and magnesium ions. But heavy metal ions or ammonium salts can also thus be bound through ion exchange.

Both reactions, water softening and the supply of alkali, are similarly rapid.

softening and the supply of alkali, are similarly rapid. An excess of water dissolves a part

An excess of water dissolves a part of the layered silicate and forms a water glass-like solution.

These simultaneous reactions make up the diverse property profile of SKS-6. This is particularly advantageous for modern detergent formulations and can be used in many ways. The final products thus manufactured with SKS-6 meet the highest demands on activity and low dosage and do not cause any adverse effects after application.

For some time there has been a demand for compact and multi- functional builders (Fig. 4). SKS-6 is non-eutrophic and leaves no water-insoluble residue in waste water treatment plants that would otherwise require a lot of resources to be separated and deposited.

Nowadays, modern detergents are usually dry-mixed instead of being spray-dried, this is a more economical process. It is necessary to have a carrier substance for this, such as SKS-6 powder, that can take up liquids such as surfactants, copolymers etc.

Particularly, modern compact detergents and detergent tablets require highly effective raw materials that can simultaneously undertake several functions, so as to lower the dosage or to create a degree of freedom for innovative formulations (Fig. 5).

Especially when used in dishwasher detergents, SKS-6 demon- strates its multifunctional character. It supplies the alkalinity necessary for the cleaning process, it binds hardness in water and from food residues, it is compatible with the carriers of active oxygen sodium perborate and sodium percarbonate and it is markedly effective against the consequences of glass corrosion. This is dealt with separately in the section “Automatic dishwasher detergents”.

fIgure 4: Why use layered silicate SKS-6?

why use layered silicate SKS-6?

· General demand for environmentally compatible and compact builders

· Modern detergents: dry mixed instead of spray dried

· Compact detergents, tablets: few ingredients, high stability

· Multifunctionality in HDP’s

· Favourable ecological profile

· Contributing to cleaning ability in ADD’s. Provides additional benefit due to its anticorrosive properties

SKS-6 can totally or partially replace

· Zeolite for water softening

· Water glass for alkalinity and protection from corrosion

· Soda ash for alkalinity and washing performance

SKS-6 can partially replace

· Polycarboxylate cobuilder

· Surfactants, due to its detergency boosting effect

fIgure 5: Why use layered silicate SKS-6?

20 10 0 Content in formula [%]
20
10
0
Content in formula [%]

Ingredients replaced

n Polycarboxylate

n Amorphous disilicate

Formula including SKS-6

n Soda

n Zeolite

n SKS-6

SKS-6

ProDuct range, PartIcle Structure anD morPhology

Today’s range of SKS-6 types comprises SKS-6 powder, SKS-6 granular, SKS-6 HD and SKS-6 HD-D (Fig. 6).

fIgure 6: Product range of SKS-6 types

tyPe

SIlIcate content

aDDItIve

mean PartIcle SIze

ProPertIeS/BenefItS

aPPlIcatIon

[%]

[

µ m]

SKS-6 PowDer

> 99

90 -150

Liquid uptake

HDPR, HDPC, HDDT

SKS-6 granular

> 96

500 -700

Flowability, kinetics,

HDPC, ADW, WS

low residue

SKS-6 hD

67-79

Polycarboxylic,

450 -700

Surfactant uptake,

ADW, HDPC, WS

acid soln.

flowability, dispersibility

SKS-6 hD-D

58 -73

Polycarboxylic, acid soln., Zn-salt

450 -700

Glass care,

ADW

décor protection

SKS-6 powder is a powder with medium-sized particles. The micro- scopic photograph shows that the surface is more fissured than that of a spray-dried disilicate (Fig. 7). Therefore it is suitable to be used as a base material for compounds with surfactants and polymers and for heavy-duty detergents, especially regular detergents. It is also suitable for water softeners.

SKS-6 granular is a pressed granulate with high bulk density and is generally post-blended in a dry mixing process in detergent production. The main applications are compact heavy-duty detergents and automatic dishwasher detergents, but also fine- fabric detergents and color detergents.

detergents and automatic dishwasher detergents, but also fine- fabric detergents and color detergents. 10 SKS®- 6

SKS-6 HD is an agglomerate of SKS-6 and a special acid copolymer. In automatic dishwasher detergents it results in an increased cleaning effect and offers protection from the consequences of glass corrosion. In general, it is suitable because of its porous structure (Fig. 7) for taking up liquid components, e.g. nonionic surfactants. This is convenient for example with heavy-duty detergents. It is particularly suitable for fine-fabric detergents because of its reduced alkalinity, which is achieved by conversion with acid co-polymer.

In water softening formulations it can act as carrier for the higher dosed copolymer solutions.

SKS-6 HD-D contains in addition to the special acid copolymer a zinc salt and is especially for use in automatic dishwasher detergents in which it provides additional glass care and décor protection.

it provides additional glass care and décor protection. fIgure 7: Morphology of various solid detergent builders

fIgure 7: Morphology of various solid detergent builders

amorPhouS DISIlIcate 200 x

SKS-6 PowDer 200 x

SKS-6 hD 100 x

fIgure 7: Morphology of various solid detergent builders amorPhouS DISIlIcate 200 x SKS-6 PowDer 200 x
fIgure 7: Morphology of various solid detergent builders amorPhouS DISIlIcate 200 x SKS-6 PowDer 200 x
fIgure 7: Morphology of various solid detergent builders amorPhouS DISIlIcate 200 x SKS-6 PowDer 200 x

SKS-6

PhySIcal anD chemIcal ProPertIeS

13

Remaining (Ca, Mg) CO 3 [mg/l]

SKS-6

water SoftenIng ProPertIeS

The layered silicate SKS-6 softens water by exchange of its sodium ions with the hardness-forming calcium and magnesium ions in tap water. When added to tap water supplied to washing machines, SKS-6 powder or granules rapidly break down into very small particles and softening takes place. SKS-6 not required for softening dissolves in the wash water. Amorphous silicates, on the other hand, work via a precipitation mechanism and exploit the solubility (law of mass action) of calcium and magnesium silicate.

In the tests carried out to determine the combined calcium and magnesium binding capacity, a defined amount of builder substance is added to synthetic hard water (see information), which is held at the specified pH during the test by continual addition of acid or alkali. After a reaction time of 10 minutes, the solution is filtered and the residual hardness of the filtrate is determined.

SKS-6 reduces the hardness of tap water already at room tempera- ture and with low initial hardness values (Fig. 8). The curves show the residual total hardness. Amorphous silicates have only limited effect as a result of their residual solubility. Residual hardness with amorphous silicates is considerably higher than with SKS-6.

One application with low initial water hardness conditions is for example automatic dishwashing. The ion exchanger in the dish- washing machine produces very soft water for the dishwasher liquor. The residual hardness and the hardness from the food residue must, however, be removed.

fIgure 8: Water softening at low water hardness

(T = 25 °C, pH = 11, t = 10 min, 50 ppm water hardness)

n

60

40

20

0

SKS-6

0 0.5 1
0
0.5
1

Builder concentration [ g/l]

n Amorphous disilicate

fIgure 9: Water softening at low water hardness

(T = 25 °C, pH = 11, t = 10 min, 100 ppm water hardness) 120 80 40
(T = 25 °C, pH = 11, t = 10 min, 100 ppm water hardness)
120
80
40
0
0
1
2
Builder concentration [ g/l]
n
SKS-6
n Amorphous disilicate
Remaining (Ca, Mg) CO 3 [mg/l]

Remaining (Ca, Mg) CO 3 [mg/l]

Remaining (Ca, Mg) CO 3 [mg/l]

Remaining (Ca, Mg) CO 3 [mg/l]

Even in the case of low water hardness, e.g. in Japan, further water-softening is recommendable.

At the upper end of the soft water range (Fig. 9-10), SKS-6 also shows exceptional softening action. Even with low additions of SKS-6, residual water hardness is reduced to less than 1° German hardness. SKS-6 combines good calcium with very good magnesium bind- ing capacity and effectively reduces total hardness. Compared with amorphous silicates, only one-third of the amount of SKS-6 is re- quired to achieve the same water softness under the specified test conditions. SKS-6 is thus three times more efficient.

test conditions. SKS-6 is thus three times more efficient. The favourable properties of SKS-6 continue in

The favourable properties of SKS-6 continue in the medium water hardness range (Fig. 11-12). The water softening capacity of amor- phous disilicates drops at higher temperatures because of the higher solubility of the silicates.

fIgure 10: Water softening at low water hardness

(T = 50 °C, pH = 11, t = 10 min, 100 ppm water hardness)

n

120

80

40

0

SKS-6

0 1 2
0
1
2

Builder concentration [ g/l]

n Amorphous disilicate

fIgure 11: Water softening at medium water hardness

(T = 25 °C, pH = 11, t = 10 min, 200 ppm water hardness)

n

250

200

150

100

50

0

SKS-6

0 2 4
0
2
4

Builder concentration [ g/l]

n Amorphous disilicate

fIgure 12: Water softening at medium water hardness

(T = 50 °C, pH = 11, t = 10 min, 200 ppm water hardness)

n

250

200

150

100

50

0

SKS-6

0 2 4
0
2
4

Builder concentration [ g/l]

n Amorphous disilicate

In the hard water range SKS-6 again demonstrates its good water softening capability. (Fig. 13)

At higher wash temperatures, the degree of softening increases further (Fig. 14). Although the water softening capability of SKS-6 is fully available at room temperature, the exchange processes on the silicate framework are accelerated at higher temperatures and increase the binding capacity of the builder. In case of amorphous disilicates, the remaining water hardness is higher at increased temperatures.

Through a broad pH range, SKS-6 shows very good softening capa- bility. It already has an optimum performance at pH 9.5 (Fig. 15), the pH value which fine-fabric detergents require. It performs very well between pH 10 and 11, the pH range that heavy-duty detergents require.

fIgure 13: Water softening at high water hardness (T = 25 °C, pH = 11, t = 10 min, 400 ppm water hardness)

fIgure 14: Water softening at high water hardness (T = 50 °C, pH = 11, t = 10 min, 400 ppm water hardness)

500 400 300 200 100 0 0 2 4 Remaining (Ca, Mg) CO 3 [mg/l]
500
400
300
200
100
0
0
2
4
Remaining (Ca, Mg) CO 3 [mg/l]
Remaining (Ca, Mg) CO 3 [mg/l]

Builder concentration [ g/l]

500

400

300

200

100

0

n SKS-6

n Amorphous disilicate

n SKS-6

0 2 4
0
2
4

Builder concentration [ g/l]

n Amorphous disilicate

Comparative tests provide information about the kinetic behaviour of detergent builders. Water softening with zeolite A and with lay- ered silicate SKS-6 (Fig. 16) is considerably more effective than with amorphous disilicate. Because of their smaller primary particle size SKS-6 granulate has a greater surface that actively participates in the chemical process than SKS-6 powder, and therefore they have advantages in kinetics.

Particularly with builders for water softeners good magnesium binding is very important. In this domain, SKS-6 yields particularly good results compared to the example with zeolite (Fig. 17). If only short application times are possible, SKS-6 granular can be used to advantage because of its very good kinetics.

Conversions of the hardness data are shown in Fig. 18.

teSt conDItIonS Conditions for figs. 8-14:

Synthetic calcium- and magnesium-containing hard water with

· 50 (German hardness range 1)

· 100 (hardness range 1)

· 200 (hardness range 2)

· 400 ppm (hardness range 3)

water hardness (Ca/Mg ratio = 39/11, 78/22, 156/44, 312/88 ppm, calculated as MCO 3 )

T = 25 °C, 50 °C

pH = 11 held constant by acid addition

t = 10 min

After filtration, the residual water hardness was determined by titration against EDTA.

fIgure 15: Remaining calcium and magnesium concentrations at various ph values

(c = 1 g/l, T = 60 °C, t = 30 min, water hardness: 225 ppm CaCO 3 , 56 ppm MgCO 3 )

fIgure 17: Magnesium binding capacity vs time (c = 1 g/l, T = 30 °C, pH = 10.5, water hardness 17 °d, Mg-sensitive electrode)

400 250 200 150 200 100 50 0 0 8 10 12 Remaining Ca resp.
400
250
200
150
200
100
50
0
0
8
10
12
Remaining Ca resp. Ca+Mg
[mg MgCO 3 /l]
MgBC [mg MgCO 3 /g]

pH value

0 5 10 Time [min]
0
5
10
Time [min]

n Ca

n Ca + Mg

n SKS-6 powder

n SKS-6 granular

n Zeolite A

fIgure 16: Calcium binding capacity of different builders

(c = 1 g/l, T = 30 °C, pH = 10.5, water hardness 17 °d, Ca-sensitive electrode)

fIgure 18: Water hardness calculation diagram (German hardness range 1: <7 °d, h.r. 2: 7–14 °d, h.r. 3: 14–21 °d, h.r. 4: >21 °d)

240 180 120 60 0 0 5 10 Time [min] n SKS-6 powder n SKS-6
240
180
120
60
0
0
5
10
Time [min]
n SKS-6 powder
n SKS-6 granular
n SKS-6 HD
n
n
Amorphous disilicate
n Zeolite A
CBC [mg CaCO 3 /g]
Degrees German water hardness [°d]
30 20 10 0 0 200 400 600 [ppm] Ca n CaO n CaCO 3
30
20
10
0
0
200
400
600
[ppm]
Ca
n CaO
n CaCO 3
n Mg
n MgO
n MgCO 3

Alkalinity and reserve alkalinity

As SKS-6 dissolves, sodium ions from the silicate framework are exchanged with protons of the water. In this way the pH of the solution is increased. With SKS-6 it is possible to achieve higher pH values than with the same amount of an amorphous disilicate (Fig. 19).

The pH increase is essentially dependent on the temperature and the water hardness. As a rule, a higher pH value can be achieved at a lower temperature because then the silicate hydrolysis reaction which uses alkalinity begins only slowly (Fig. 20). In tap water the pH increase is somewhat delayed compared with pure water, because the exchanged alkaline earth ions stabilise the layer lattice and thus slightly delay the disintegration of the silicate.

The silicate lattice counteracts a decrease of the pH value, as can be seen when acid is added (Fig. 21). Of all tested builders, SKS-6 has the greatest buffer range of pH values higher than 8, followed by amorphous silicate mr 2.65. Because of their molecular structure, amorphous disilicates cannot make equal quantities of alkali avail- able. The silicate structure is also not able to counter pH reduction as SKS-6 does. As a compound of SKS-6 and acid copolymer SKS-6 HD deliberately contains a lower buffering effect. Phosphate and zeolite show only a low buffering effect.

fIgure 19: pH value vs time (c = 1 g/l, T = 25 °C, deionized water)

12

10 8 0 5 10 15 pH value
10
8
0
5
10
15
pH value

n SKS-6 granular

Time [ min ]

n Amorphous disilicate granular

If one then compares the amount of alkali that the builder in effect makes available

If one then compares the amount of alkali that the builder in effect makes available with the two pH values of 10 and 9.5 (Fig. 22) it becomes apparent that zeolite is not effective. Disilicate has a noticeable buffering effect. In the soda/ disilicate compound it is particularly the soda that is effective. In comparison SKS-6 is the best alkali supplier.

Besides others, the pH of the wash liquor is a crucial factor affecting the efficiency of the washing process. A builder with reserve alka- linity has advantages here, since it can counter the effect of acid soil particles and enhance soil removal. Furthermore, acid components added in the detergent manufacturing process can be neutralised. Especially in compact detergents, SKS-6 can therefore be used as a replacement for a part of the soda and the amorphous silicate.

SKS-6 acts as a pH regulator and buffer, even in low amounts. This is of particular interest in regions where detergents are traditionally used in low concentrations or, for example, in dishwashing agents.

fIgure 20: pH value of SKS-6 vs time and water hardness

(c = 10 g/l, tap water 17 °d)

13

11 9 0 5 10 15 pH value
11
9
0
5
10
15
pH value

n Deionised water 20 °C n Deionised water 60 °C

Time [ min ]

n Tap water 20 °C n Tap water 60 °C

fIgure 21: Reserve alkalinity of detergent builders

(c = 1 g/l, T = 20 °C, deionized water, titration with 0.1 N HCl solution)

12 8 4 0 0 6 12 pH value
12
8
4
0
0
6
12
pH value

n SKS-6 powder n SKS-6 granular n SKS-6 HD

NaOH equivalent [ mmol ]

n Zeolite A n Amorphous silicate mr 2.65 n Sodium tripolyphosphate

fIgure 22: Reserve alkalinity of various detergent builders

(c = 0.02 %, T = 20 °C, t = 20 min, titration with 0.1N HCl, r.a. calculated as NaOH,

corresponding to the amount of acid required to set a pH value of 10.0 resp. 9.5)

40 30 20 10 0 SKS-6 SKS-6 HD Amorphous Soda/ Zeolite A disilicate disilicate cpd.
40
30
20
10
0
SKS-6
SKS-6 HD
Amorphous
Soda/
Zeolite A
disilicate
disilicate
cpd.
pH = 10
n
pH = 9.5
Alkali equivalent [ % ]
Dispersed particle size, solubility and dispersing properties When SKS-6 is added to water, it breaks

Dispersed particle size, solubility and dispersing properties

When SKS-6 is added to water, it breaks down into very fine par- ticles due to chemical reactions previously described in chapter »SKS-6 characterisation«. The exchange of sodium ions for calcium and magnesium ions on the newly created surface begins immedi- ately. The process is so quick, that within several minutes SKS-6 has dispersed into microscopically small particles of the size of about five to fifteen microns, according to the relevant water hardness (Fig. 23). Because of the grinding action during the compaction process, SKS-6 granular contains smaller primary particles, so the process here is even faster.

Parallel to the disintegration of the disilicate particles, the alka- line environment can slowly attack the silicate framework. There- by small fragments of the silicate layers dissolve as water glass type chemical species. According to the hardness of the water used the speed of the process varies (Fig. 24-25). Important is the stabilising influence of the hardness ions on the silicate structure. The alkaline earth ions remain bound, they cannot cause any carbonate precipi- tation. Ideally, the silicate share is dissolved which is not needed for softening.

fIgure 23: Dispersed particle size of different SKS-6 types vs time and water hardness

(T = 20 °C)

80

40 0 0 5 10 Time [ min ] n SKS-6 granular 0 °d n SKS-6 granular 17 °d
40
0
0
5
10
Time [ min ]
n SKS-6 granular 0 °d
n SKS-6 granular 17 °d
n SKS-6 powder 0 °d
n SKS-6 powder 17 °d
Mean particle size [μm]

fIgure 24: SKS-6 solubility vs time

(c = 2 g/l, deionized water)

100 50 0 0 15 30 45 Solubility [%]
100
50
0
0
15
30
45
Solubility [%]

n SKS-6 granular 20 °C n SKS-6 granular 60 °C

Time [min]

n SKS-6 powder 20 °C n SKS-6 powder 60 °C

The influence of temperature is also significant (Fig. 26). Hydrolysis increases with the temperature.

Traditionally, liquid or spray-dried water glass is added to deter- gents to support the dispersing of dirt particles in the wash liquor and to achieve a certain effect of protection against corrosion. This function can be taken over by the parts formed through the hydrolysis of SKS-6 that are similar to water glass (Fig. 27).

fIgure 25: SKS-6 solubility vs time

(c = 2 g/l, tapwater 17 °d)

100

50 0 Solubility [ % ]
50
0
Solubility [ % ]
0 15 30 45 Time [ min ] n SKS-6 granular 20 °C n SKS-6 granular 60 °C n
0
15
30
45
Time [ min ]
n SKS-6 granular 20 °C
n SKS-6 granular 60 °C
n SKS-6 powder 20 °C
n SKS-6 powder 60 °C
fIgure 26: Solubility of SKS-6 vs temperature
(c
= 10 g/l, T = 15 min, water hardness 17 °d)
100
50
0
20
60
100
Solubility [ % ]

Temperature [ °C ]

fIgure 27: Dispersing effect of silicate builders

(c = 0.5 %, T = 20 °C, t = 2 h, pH = 10, water hardness 23 °d,

0.5 % pigment Bayferrox 130, “Schwarzband” filtration paper)

80 40 0 SKS-6 HD SKS-6 granular Amorphous disilicate Dispersing effect [ % ]
80
40
0
SKS-6 HD
SKS-6 granular
Amorphous disilicate
Dispersing effect [ % ]

mr 2.65

Storage properties

Among the most important properties of detergent raw materials are the storage properties. These include the storage stability of the product itself, i.e. the tendency to form lumps, caking etc. as well as the deterioration of the properties of other detergent ingredients.

The storage stability in silos for example can be characterised by means of ring shear measurements according to Dr. Schulze, a modification of the Jenicke principle. Essentially a material sample is compacted in a ring-type measuring cell (consolidation stress). Then the sample is released and sheared by means of an applied force, i.e. it is brought to a flowing movement. The flowability of a sample under applied pressure, here the ff c value, is the unconfined yield strength in relation to the consolidation stress.

In a time-dependent study, one finds that SKS-6 granular and SKS-6 HD are still easily flowing even after being stored under pressure for one week (Fig. 28). This is an advantage for silo storage. Zeolite is already in the cohesive range at the start and hardens even more after a certain time. SKS-6 powder shows a certain storage consolidation, but it is better than zeolite.

Water uptake

With modern detergents high demands are made on the perfor- mance of the bleaching system and on the handling capability. Free moisture in powder-type products interferes with the handling properties and destabilises the bleaching system in particular. Detergent raw materials, that do not contain any moisture them- selves, but can bind moisture, have a great advantage.

As a comparison shows, SKS-6 in powder form as well as in granu- late or compound form can take up high amounts of humidity (Fig. 29). The uptake depends on the partial pressure of water vapour. If the relative humidity is low at lower temperatures, less water is taken up, if a lot of water is available then correspondingly more moisture is absorbed (Fig. 30).

then correspondingly more moisture is absorbed (Fig. 30). fIgure 28: Storage behaviour of various builder types

fIgure 28: Storage behaviour of various builder types (flowability ring shear test at a consolidation strength sigma1 = 22 kPa; 10 < ff c : free flowing, 4 < ff c < 10: easily flowing, 2 < ff c < 4: cohesive)

40

20 0 0 4 8 Storage time [ d ] n SKS-6 HD n SKS-6 granular n
20
0
0
4
8
Storage time [ d ]
n SKS-6 HD
n SKS-6 granular
n SKS-6 powder
n Zeolite A
ff c value

fIgure 29: Water content of SKS-6 types vs time (T = 20 °C, 95 % rH)

10

5 0 Absorbed mass water [ % ]
5
0
Absorbed mass water [ % ]
0 50 100 150 200 Time [ h ] n SKS-6 powder n SKS-6 HD n SKS-6
0
50
100
150
200
Time [ h ]
n
SKS-6 powder
n SKS-6 HD
n SKS-6 granular
fIgure 30: Water uptake of SKS-6 powder
(stop period: 3.8 d, ambient temperature)
8
6
4
2
0
50
100
Absorbed mass water [ % ]

Relative humidity [ % ]

Surfactant uptake

fIgure 31: Surfactant uptake of SKS-6 powder vs flowability (10 < ff c : free flowing, 4 < ff c < 10: easily flowing, 2 < ff c < 4: cohesive)

8

4 0 0 10 20 ff c value
4
0
0
10
20
ff c value

Nonionic surfactant content in compound [ % ]

fIgure 32: Surfactant uptake of various detergent builders (Genapol OA 080, gravity-flow mixer)

20 10 0 SKS-6 Amorphous Zeolite A SKS-6 Soda/ powder disilicate powder granular disilicate cpd.
20
10
0
SKS-6
Amorphous
Zeolite A
SKS-6
Soda/
powder
disilicate
powder
granular
disilicate cpd.
powder
granule
Nonionic surfactant content
in compound [ % ]

In the modern detergent production process, the components are mixed in a free-flowing state. This is energy-saving since, in contrast to the slurry method of manufacture, no water is evaporated.

Through suitable process control, detergents with high bulk density are obtained, which satisfy today’s requirements for compactness. The product should have a very good appearance and be free-flow- ing. Since individual components (e.g. surfactants) are liquid or hydrous, constituents are required that have high absorption capacity. Substances that not only act as carriers but are multifunc- tional offer a particular advantage. SKS-6 is such a substance and combines high calcium binding capacity and pH buffering with high absorption capacity for liquid components, e.g. surfactants.

The high surfactant absorption capability of SKS-6 can be demon- strated. For this purpose, SKS-6, a number of other silicates and zeolite were sprayed with various surfactants in different mixer systems.

With SKS-6 powder, compounds can be manufactured with non- ionic surfactants that are still easily flowing. This can be shown with the help of shear measurements based on the Jenicke principle (Fig. 31).

If other builders are also sprayed with surfactant at a predeter- mined flowability (free-flowing properties according to DIN 53916) in a gravity-flow mixer, the amounts of surfactant taken up vary con- siderably (Fig. 32). Genapol OA 080 is an alkyl ethoxylate based on C14/C15-oxoalcohol. It contains eight units of ethylene oxide and is frequently used as a nonionic surfactant in detergent formulations.

Among the favourites of the investigated products are powder- type SKS-6 and amorphous disilicate, whereas

Among the favourites of the investigated products are powder-

type SKS-6 and amorphous disilicate, whereas zeolite powder has

a markedly poorer result. Because of the more porous morphology

of builder powder, its absorption capacity is in general higher than that of builder granules. These have a more compact surface and

a denser internal structure. SKS-6 granules, however, can absorb more surfactant than soda/disilicate granules.

In the detergent manufacturing process, the use of ploughshare mixers is also typical. In these mixers, high shear stresses act on the components. Under these conditions, SKS-6 powder absorbs much more LAS – linear alkyl benzene sulfonate – than zeolite A powder and sodium tripolyphosphate (Fig. 33). When SKS-6 is used, a uniform, granulated, free-flowing product according to DIN 53916 is obtained without lumps or caking.

The flowability of compounds with LAS can be further improved by the use of SKS-6 powder with a smaller particle size (Fig. 34).

fIgure 33: Surfactant uptake of various detergent builders (LAS, ploughshare mixer)

30 20 10 0 SKS-6 Zeolite A Sodium triphos- powder powder phate powder Nonionic surfactant
30
20
10
0
SKS-6
Zeolite A
Sodium triphos-
powder
powder
phate powder
Nonionic surfactant content
in compound [ % ]

fIgure 34: Surfactant uptake and flowability (Compounds of 30 % LAS with different particle size fractions of 70 % SKS-6 powder, flowability tests in ring shear tester; 10 < ff c : free flowing, 4 < ff c < 10:

easily flowing, 2 < ff c < 4: cohesive) 12 8 4 0 0 500
easily flowing, 2 < ff c < 4: cohesive)
12
8
4
0
0
500
1000
ff c value

All material through sieve size [ μm ]

fIgure 35: Surfactant uptake of SKS-6 HD vs flowability (10 < ff c : free flowable, 4 < ff c < 10: easily flowable, 2 < ff c < 4: cohesive)

60 40 20 0 SKS-6 HD SKS-6 HD + 25 % nonionic surfactant SKS-6 HD +
60
40
20
0
SKS-6 HD
SKS-6 HD
+ 25 % nonionic
surfactant
SKS-6 HD
+ 30 % nonionic
surfactant
ff c value

Surfactant compounds of SKS-6 HD, the granulate made from SKS-6 and acid copolymer (Fig. 35) are particularly easy to handle. It is possible to add e.g. 30 % alkylethoxylate without affecting the good flowability.

Compatibility with other

Detergent IngreDIentS

A detergency builder must not

only achieve good water softening,

it has to be compatible with the

sensitive detergent additives.

fIgure 36: Active oxygen stability of SKS-6 based detergent formulas

 

1 [%]

2 [%]

3 [%]

4 [%]

SKS-6 granular*

44.3

27.2

zeolIte a

17.1

44.3

zeolIte P

44.3

PercarBonate 25.7, SoDa 22.9, PeractIve an* 7.1 %

* Clariant product brand names

fIgure 37: Active oxygen stability of SKS-6 based detergent formulas (T = 37 °C, 67 % rH, in open plastic bottles)

100 50 0 0 5 10 15 Time [ d   ] n 1 SKS-6 n 2 Zeolite
100
50
0
0
5
10
15
Time [ d   ]
n 1 SKS-6
n 2 Zeolite A + SKS-6
n 3 Zeolite A
n 4 Zeolite P
Active oxygen decay [ % ]

Best known is the destruction of the bleaching system caused by the release of humidity. Such an effect is best demonstrated by practical formulations (Fig. 36) that are stored under forced ambient condi-

tions. These include elevated temperature and increased air humid-

ity. The characteristic factor for the bleaching system is the active

oxygen content.

Zeolite A used as sole builder effects a complete decomposition of the bleaching system after only a short storage time (Fig. 37). Because it is water free and due to its humidity buffering property SKS-6 in a binary zeolite/SKS-6 builder system can have a stabilis- ing effect. Zeolite P has a lesser water of crystallisation share than zeolite A and has better results. SKS-6 used alone has the best results; the bleaching system is attacked only very slowly.

better results. SKS-6 used alone has the best results; the bleaching system is attacked only very

fIgure 38: Active oxygen stability of SKS-6 based detergent formulas

 

5 [%]

6 [%]

7 [%]

8 [%]

SKS-6 granular*

30

12

zeolIte a

20

30

zeolIte P

30

SoDa

15

4

15

15

Sulfate

9

18

9

9

Percar B onate 20, laS 12, g ena P ol oa 3070* 7, Peract Ive an * 4, PolycarBoxylate 3 %

* Clariant product brand names

The same picture is obtained when complete basic heavy-duty formulations are investigated (Fig. 38). The order of stability in the bleaching system remains unchanged (Fig. 39). The most rapid decomposition is achieved with Zeolite A. In combination with SKS-6 a certain improvement is possible. Zeolite P has moderate results and SKS-6 shows in comparison the best compatibility with the bleaching system.

Of interest is also a comparison of SKS-6, SKS-6 HD and zeolite. In one study, the three builders were integrated in heavy-duty formulations (Fig. 40) and exposed to elevated temperature alone as well as in combination with increased humidity.

Zeolite A already shows a noticeable decrease of the bleaching system without exposure to humidity (Fig. 41). This is a clear indication of the mobility of the zeolite water of crystallisation. Exposure to humidity increases the decomposition of the percarbonate.

fIgure 39: Active oxygen stability of SKS-6 based detergent formulas (T = 37 °C, 67 % rh, in open plastic bottles)

100 50 0 Active oxygen decay [ % ]
100
50
0
Active oxygen decay [ % ]
 

0

5

10

15

 

Time [ d ]

 

n 5 SKS-6

n 6 Zeolite A + SKS-6

n 7 Zeolite A

n 8 Zeolite P

 

fIgure 40: Active oxygen stability of SKS-6 based detergent formulas

 
 

9 [%]

10 [%]

 

11 [%]

SKS-6 granular*

 

40

 

25

 

SKS-6 hD*

 

 

20

 

zeolIte a

   

 

 

40

PolycarBoxylate

 

5

 

 

5

PercarBonate 20, laS 9, genaPol oa 080* 8, PeractIve an* 5, enzyme 2, antIfoam 1, Sulfate to 100 %

* Clariant product brand names

fIgure 41: Active oxygen stability of SKS-6 HD based detergent formulas (closed storage: glass bottle, 30 °C; open storage: wax carton, 30 °C, 70 % rh)

100 50 0 9 SKS-6 granular 10 SKS-6 granular + SKS-6 HD 11 Zeolite A
100
50
0
9 SKS-6 granular
10 SKS-6 granular
+ SKS-6 HD
11 Zeolite A
n 7d closed
7d open
Active oxygen decay [%]

Precipitation and

InorganIc IncruStatIonS

It was recognized early on that silicates in the form of water glass could bind the hardness-forming calcium and magnesium ions of tap water. In this process, the hardness salts are removed as a precipitate. The disadvantage is that the precipitate is flocculent and bulky and forms incrustations on the laundry fabrics. These make the laundry feel hard, cause fibre wear and lead to rapid greying of light-coloured textiles.

Softening with amorphous disilicates in powder or granule form employs this precipitation mechanism. First of all, the solid silicate dissolves and forms flocculent, white precipitates. The water hardness is thus removed from the wash liquor. If the precipitate is filtered and dried, hard and solid compounds are obtained (Fig. 42).

Another possible way of precipitating calcium and magnesium ions is the reaction with soda. This accelerates what also happens in tap water through reaction of the constituents on heating: calcium carbonate – lime – is precipitated. Silicate can be added with the intention to influence crystallisation and keep the precipitate in suspension. In dried form, this precipitate is also hard and solid.

SKS-6, on the other hand, binds the hardness of tap water by ex- changing calcium and magnesium ions for sodium ions. SKS-6 powder or granules rapidly break down in the water into microscop- ically small particles on which the softening process takes place. The silicate particles saturated with hardness ions have a self- dispersing effect and remain in suspension until the wash liquor is rinsed out.

Zeolite A also softens water by ion exchange. The insoluble zeolite is uniformly suspended in the wash liquor and takes up the hardness ions as solids. To prevent its depositing on the fibres or in the wash- ing machine, polycarboxylate-based dispersants must be added.

fIgure 42: Morphology of precipitates of various builders (water hardness: 400 ppm CaCO 3 , magnification 50 x)

SKS-6

amorPhouS DISIlIcate

zeolIte a

SoDa/DISIlIcate comPounD

400 ppm CaCO 3 , magnification 50 x) SKS-6 amorPhouS DISIlIcate zeolIte a SoDa/DISIlIcate comPounD 28 SKS®- 6
400 ppm CaCO 3 , magnification 50 x) SKS-6 amorPhouS DISIlIcate zeolIte a SoDa/DISIlIcate comPounD 28 SKS®- 6
400 ppm CaCO 3 , magnification 50 x) SKS-6 amorPhouS DISIlIcate zeolIte a SoDa/DISIlIcate comPounD 28 SKS®- 6
400 ppm CaCO 3 , magnification 50 x) SKS-6 amorPhouS DISIlIcate zeolIte a SoDa/DISIlIcate comPounD 28 SKS®- 6

In practice, such incrustations of lime from the water hardness and from residue of insoluble builders appear especially on the heating coils of washing machines or on textiles. If repeated heating cycles in washing machines are simulated (Fig. 43-44), noticeable residue is found already after several washing cycles. After a longer, repeat- ed use soda/disilicate compound leaves the most noticeable residue followed by amorphous disilicate and zeolite. The least deposits result from the use of SKS-6. In the case of soda/ disilicate compound, the deposits are mainly precipitated lime (Fig. 45). Apart from precipitated magnesium silicate and lime, amorphous disilicate seems also to be subject to hydrolysis to silicic acid. Above all, SKS-6 shows small quantities of not completely bound calcium carbonates.

small quantities of not completely bound calcium carbonates. fIgure 43: Precipitates on heating coils (c =

fIgure 43: Precipitates on heating coils (c = 1 g/l builder, 0.1 g/l Sokalan CP 5; T = 60 °C, 30 min per heating cycle, water hardness: 80 mg/l Ca, 15 mg/l mg and 0.02 % CO 2 )

0.4

0.2 0 0 10 20 Weight increase [g]
0.2
0
0
10
20
Weight increase [g]

n SKS-6 n Amorphous disilicate

Heating cycles

n Zeolite A n Soda/disilicate cpd.

fIgure 44: Precipitates on heating coils

SoDa/DISIlIcate

amorPhouS

comPounD

DISIlIcate

SKS-6

amorPhouS comPounD DISIlIcate SKS-6 fIgure 45: Composition of precipitates on heating coils 1.2

fIgure 45: Composition of precipitates on heating coils

1.2 0.8 0.4 0 Soda ash/ Amorphous SKS-6 disilicate cpd. disilicate MgSi 2 O 5
1.2
0.8
0.4
0
Soda ash/
Amorphous
SKS-6
disilicate cpd.
disilicate
MgSi 2 O 5
n CaCO 3
n SiO 2
Composition [%]

fIgure 46: Comparison of the morphologies of residues of various builders on fabrics (magnification 2000 x)

SKS-6

amorPhouS DISIlIcate

SoDa/DISIlIcate comPounD

SKS-6 amorPhouS DISIlIcate SoDa/DISIlIcate comPounD Incrustations also appear on the washed fabrics (Fig. 46).
SKS-6 amorPhouS DISIlIcate SoDa/DISIlIcate comPounD Incrustations also appear on the washed fabrics (Fig. 46).
SKS-6 amorPhouS DISIlIcate SoDa/DISIlIcate comPounD Incrustations also appear on the washed fabrics (Fig. 46).

Incrustations also appear on the washed fabrics (Fig. 46). With the pure silicates rather even incrustations occur, like a covering, whereas crystal-like deposits develop with soda/disilicate com- pound.

If one compares zeolite and zeolite/SKS-6 systems (Fig. 47), it becomes obvious that the main residue of the zeolite-based systems consists of zeolite itself (Fig. 48). A combined zeolite/SKS-6 system shows a markedly lower zeolite residue.

fIgure 47: Detergent formula for evaluation of inorganic incrustations composition

 

1 [%]

2 [%]

zeolIte a

31

19

SKS-6 granular*

12

amorPhouS DISIlIcate

3

SoDa

13

16

PolycarBoxylate 5, PerBorate · h 2 o 18, PeractIve an* 5, laS 10, genaPol oa 080* 8, SoaP 2, antIfoam 1, enzymeS 3, oPtIcal BrIghtener 0.5, PhoSPhonate 0.5 %

* Clariant product brand names

 
fIgure 48: Composition of inorganic incrustations on fabrics 6 4 2 0 1 Zeolite 2
fIgure 48: Composition of inorganic incrustations on fabrics
6
4
2
0
1 Zeolite
2 Zeolite
Commercial brand
+ SKS-6
CaCO
n CaSiO 3
n Zeolite
3
Composition [%]

Heavy metal

BInDIng caPacIty

Because of their negative influence on the stability of bleaching systems and their damaging effect on textile material, one endeav- ours to bind heavy metal traces in detergents. Besides chelating agents such as EDTA or phosphonates, SKS-6 can also take over the function of a heavy metal scavenger. SKS-6 binds the interfering heavy metal ions in the wash liquor by means of the same ion exchange mechanism as the hardness ions.

Ion exchange is more effective than just a precipitation, as the following comparison of SKS-6, amorphous disilicate and soda/ disilicate compound shows. For this the binding capability of manganese and copper in soft, medium hard and hard water is determined. In soft water the heavy metal binding capacity of SKS-6 is higher than that of amorphous disilicate. Both show a preference for manganese (Fig. 49). The soda/disilicate compound has the poorest heavy metal binding capacity.

In medium hard water SKS-6 binds heavy metal ions almost com- pletely. Here amorphous disilicate is markedly better than in soft water. The soda/disilicate compound gives the poorest results. The good effect of SKS-6 and the behaviour of amorphous disilicate and soda/disilicate compound can be explained by the fact that with SKS-6 the heavy metal traces are removed by ion exchange, whereas with amorphous disilicate and soda/disilicate compound there has to be a precipitation of heavy metal and silicate. In soft as well as in medium hard water the solubility products heavy metal/carbonate or heavy metal/silicate have not yet been exceeded, for this reason there is no precipitation.

In hard water conditions SKS-6 eliminates heavy metals almost completely, and amorphous disilicate and soda/disilicate compound also perform better than in less hard water.

fIgure 49: Heavy metal binding capacity vs artificial water hardness (T = 25 °C, t = 10 min, pH = 10)

100 50 0 0 200 400 HMBC [%]
100
50
0
0
200
400
HMBC [%]

n SKS-6: Cu n SKS-6: Mn n Amorphous disilicate: Cu

water hardness [ppm]

n Amorphous disilicate: Mn n Soda/disilicate cpd.: Cu n Soda/disilicate cpd.: Mn

teSt conDItIonS

Heavy metal concentration:

0.02 ppm Mn, 3 ppm Cu

Addition of builder and water hardness:

· 0.5 g/l and 0 ppm water hardness

· 0.5 g/l and 100 ppm water hardness (78 ppm CaCO 3 plus 22 ppm MgCO 3 )

· 1 g/l and 400 ppm water hardness (312 ppm CaCO 3 plus 88 ppm MgCO 3 )

· Ca and Mg used as chlorides

pH value: 10.0

Trial period: 10 min

Temperature: 25 °C

SKS-6

envIronmental anD Safety aSPectS

33

Life cycle

Inventory

Apart from many other attempts to judge detergent ingredients from an ecological point of view, in recent times the process of ecological inventory (life cycle inventory) has entered the discus- sion. This involves the compilation of environmental influences of the manufacture of a product in the form of material and energy balances.

Based on data from the production of amorphous sodium disilicates, the SKS-6 production was inventoried. This was done in the sense of a »cradle to factory gate« study, i.e. the use of SKS-6 in detergents and their disposal was not included (Fig. 50).

fIgure 50: Selected data from the SKS-6 life cycle inventory (data per t anhydrous material)

6

4

2

0

Total raw material consumption [t/t]

Total water consumption [m 3 /t]

Total delivered energy [10 GJ/t]

Emissions CO 2 [t/t]

Emissions inorg. salts + acids [kg/t]

Solid waste

[10 kg/t]

Solubility

In waSte water

Modern detergents should not only offer good performance properties, they must also have as less of impact on the environment as possible. Besides economical use of energy in raw material manufacture, formulation, production, distribution and washing processes, the behaviour of the detergent components in waste water treatment plants and in rivers and lakes is particularly important.

In the washing process, SKS-6 breaks down into numerous, micro- scopically small particles, which bind the hardness ions. These saturated silicate particles remain dispersed in the wash liquor. Any SKS-6 not required for water softening dissolves in the wash liquor. This wash liquor is diluted in time to a ratio of about 10 : 1 by the washing machine rinsing water and other quantities of household water prior to discharge into the sewerage system (Fig. 51). As this water then makes its way to the sewage treatment plant, it is calcu- lated that further dilution to a ratio of about 40 : 1 takes place. On the way to the treatment plant, the layered silicate particles loaded with calcium and magnesium break down into their basic chemical constituents, which remain dissolved in the water. In the treatment plant, the original solution is finally diluted to about 100 : 1.

In our own study of this process, laundering trials were carried out at wash temperatures of 30 °C and 60 °C and dissolving behav- iour was studied. The resulting wash liquor and first rinsing water together were diluted 10 times and 40 times. This process simulates the dilution in municipal sewerage systems which takes place between the household and the treatment plant. Measurements were carried out after one and six hours according to the average residence times in the sewerage system in order to identify any time-dependency of solubility behaviour.

At 30 °C wash temperature, the dissolved silicate content in the mixture of wash liquor and first rinsing water is 30 % after one hour (Fig. 52).

teSt conDItIonS

Washing machine: Miele Novotronic W 917

Washing programme: single wash cycle

Wash temperatures: 30 °C, 60 °C

Water hardness: 18 ° German hardness = hardness range 3 (Ca : Mg = 3 mol : 1 mol)

Laundry: 4.5 kg (clean)

Detergent: dosage 100 g

Content of SKS-6 = 40.8 %

fIgure 51: Dilution of household waste water in sewerage system

washing machine

wash liquor + 1 st rinsing water

Initial conc.

Dilution 10 : 1

Dilution 40 : 1

additional household waste water

additional water on way to treatment station

treatment plant

When the wash liquor and rinsing water are diluted with additional water to a ratio of 10 : 1, the dissolved content increases to 50 % as

a result of the dilution alone. The effect of the residence time can

be seen after 6 hours – then 75 % of the silicate is dissolved. When the mixture of wash liquor and rinsing water is diluted to 40 : 1, the dissolved silicate content is 90 % after one hour and 100 % after

a residence time of six hours.

The influence of temperature on solubility can be seen at 60 °C wash temperature. The soluble silicate content in the wash liquor and first rinsing water after one hour is 60 %. This means that the hydrolytic degradation is higher at 60 °C wash temperature.

On dilution with water to a ratio of 10 : 1, the soluble silicate content increases after one hour to 75 %. Residence time at this wash temperature has a less pronounced effect. After six hours, the soluble content increases to 80%.

fIgure 52: Solubility of SKS-6 in waste water

100 50 0 1 20 40 Dissolved contents [%]
100
50
0
1
20
40
Dissolved contents [%]

Dilution [Initial conc., 1 : 10, 1 : 40]

n 30 °C, 1 h n 30 °C, 6 h

n 60 °C, 1 h n 60 °C, 6 h

In a 40 : 1 solution, silicate solubility after one hour has increased to 90 %. After six hours, all the silicate (100 %) is dissolved. The chemical breakdown of SKS-6 into a soluble form is influenced by three parameters: wash temperature, dilution and residence time.

As a detergent builder, SKS-6 appears to have very good performance properties and also good ecological properties. The results of this model study show that SKS-6 dissolves after washing before it reaches the municipal waste-water treatment plant. Thus it behaves ecologically like water glass, which has been used in detergents for many decades. Through hydrolytic degradation SKS-6 also loses, along with its ion binding power, a potential capacity to mobilise heavy metals from sediments. To the best of our present knowledge, the entry of soluble silicates into surface waters does not contribute to eutrophication.

Exposure

moDellIng

With the help of model calculations it is possible to estimate the change of silicate concentrations in the waste water system as well as in rivers that are the result of the market share of detergents containing SKS-6.

The study begins with the basic concentration of silicate in tap water. During the washing process in the household the detergent is mixed with tap water. The waste water is passed into the sewer- age system and then into the waste water treatment plant.

The water of the treatment plant is diluted with additional river water when it is passed into the rivers. On the assumption of an equal and ideal distribution of the silicates originated from the detergent, the concentration of the silicate is shown as a function of the dilution. This calculation is made for two different SKS-6 concentrations in detergents (15 and 40 %) and for different market shares of the relevant SKS-6-containing detergents (0 % market share corresponds to f m  = 0 and 100 % corresponds to f m  = 1).

The concentration effects that occur are small in the case of high dilution (big or normal river respectively) (Fig. 53–54), and even in the case of a stream with a dilution of one to ten and with 100 % market share of SKS-6-containing detergents, the silicate concen- tration does not increase very noticeably.

fIgure 53: Silicate input depending on SKS-6 based detergent market share f m (SKS-6 in det. 15 %, det. consumption 16 g/cap·day, typical dilution values: big river: 0.00016, river: 0.014, stream: 0.11)

4

2 0 0 0.2 0.4 Dilution in river n f m = 0 n f
2
0
0
0.2
0.4
Dilution in river
n f m = 0
n f m = 0.2
n f m = 0.4
n f m = 0.6
n f m = 0.8
n f m = 1
SiO 2 conc. by det. [ppm]

fIgure 54: Silicate input depending on SKS-6 based detergent market share f m (SKS-6 in det. 40 %, det. consumption 14 g/cap·day, typical dilution values: big river: 0.00016, river: 0.014, stream: 0.11)

8

4 0 0 0.2 0.4 Dilution in river n f m = 0 n f
4
0
0
0.2
0.4
Dilution in river
n f m = 0
n f m = 0.2
n f m = 0.4
n f m = 0.6
n f m = 0.8
n f m = 1
SiO 2 conc. by det. [ppm]

Toxicology of SKS-6 and SKS-6 based detergent formulations

The usual toxicological data were established for SKS-6. Only the eye irritation test gives cause for classification Eye damage 1 as there is a risk of serious eye damage (Fig. 55). Therefore it is recom- mended on principle to use safety glasses, face protection and rubber gloves when handling SKS-6 and to also wear a dust mask as protection in the case of exposure to dust.

Beside the properties of SKS-6 on its own it is of interest to study the properties of SKS-6 containing products as well. Their results may well differ from those that are reached with the mathematic evaluation according to the Dangerous Substances Directive.

The skin compatibility tests were carried out as Human Single Patch Test using a one percent aqueous dispersion of the detergent, and skin redness was evaluated after 24, 48 and 72 hours. Investigations of eye irritation were carried out as Low Volume Eye Test with 10 μl detergent, and the eye irritation was evaluated after 1, 24, 48 and 72 hours.

Investigations were carried out on three ultracompact detergents with builder components SKS-6, soda and bicarbonate as well as SKS-6, zeolite, soda and citric acid, a regular detergent with builder components SKS-6 and bicarbonate and two branded detergents (Fig. 56).

Formulations with SKS-6, soda and bicarbonate did not cause any eye irritation. Despite the known alkaline effect of SKS-6 the tested ultracompact and regular formulations were shown to be as advantageous with regard to skin irritation as recognised branded detergents, despite the fact that they contain a very high concentra- tion of SKS-6.

fIgure 55: Toxicology data and classification of SKS-6 InveStIgatIon ProceDure   reSult  

fIgure 55: Toxicology data and classification of SKS-6

InveStIgatIon

ProceDure

 

reSult

 

claSSIfIcatIon

ameS teSt

not mutagenic

 

algae toxIcIty

OECD 201

 

NOEC 18 mg/l

 

BacterIa toxIcIty

OECD 209

 

Na-form: EC 50 720 mg/l

DaPhnIa toxIcIty

OECD 202

 

EC 50 491 mg/l

 

eye IrrItatIon, raBBIt

OECD 405

 

irritant

 

Eye dam. 1, H318

fish toxicity

OECD 203

 

LC 50 > 500 mg/l

 

InhalatIon tox. (rat, acute)

OECD 403

 

> 3510 mg/m 3

 

oral toxIcIty (rat, acute)

OECD 401

 

LD 50 > 2000 mg/kg

 

Plant growth

EC 0 200 kg/ha

 

SenSItIzatIon

OECD 429

 

non sensitizing

 

SKIn IrrItatIon, raBBIt

OECD 404

 

non irritant

 

fIgure 56: Toxicology of SKS-6 based detergent formulas

 

conStItuentS

SKS-6 BaSeD formulaS [%]

 

commercIalDetergent

 

Ultracompact

 

Regular

   

SKS-6

50

30

15

21.3

   

zeolite a

15

   

SoDa

1.3

21.3

11.5

   

BIcarBonate

15

15

6.7

   

cItrIc acID

6

Nr. 1

Nr. 1

PercarBonate

20

20

20

25

   

taeD

5

2.2

   

anIonIcS

8

   

nonIonIcS

9.5

9.5

9

4.4

   

PolycarBoxylateS

2.5

2.5

4.5

   

otherS

1.7

1.7

6

40.4

   

low vol. eye teSt

non irritant

non irritant

not det.

not det.

not det.

not det.

SKIn IrrItatIonS (24 h)

0

not det.

2

1

3

6

SKS-6

launDry DetergentS

SKS-6 launDry DetergentS 40 SKS®- 6
41

Basic detergent effects

SKS-6 is a modern builder and can perform numerous functions in detergent formulations. We therefore call it a multifunctional builder.

SKS-6 removes the water hardness ions during washing and assists the action of the surfactants. Owing to its reserve alkalinity, SKS-6 assists detergency by providing alkalinity and compensating for fluctuations in pH value. Because of its silicate components, SKS-6 can also have a corrosion- inhibiting action and dispersing properties.

When dissolved in water SKS-6 breaks down into microscopically small layered silicate particles, which have self-dispersing proper- ties in the wash liquor. The particles charged with water hardness ions remain suspended in the wash liquor. As a detergent builder, SKS-6 therefore basically requires less dispersing additives. The addition of polycarboxylates (PCA) to detergents formulated with SKS-6 is therefore reduced.

The addition of polycarboxylates (PCA) to detergents formulated with SKS-6 is therefore reduced. 42 SKS®- 6

Coefficient, standardised

teSt conDItIonS

Miele W 917, main wash programme, 60 °C, 18 °d, dosage 75 g, 25 wash cycles

Wash effect: test fabrics EMPA 104, WFK 10D

Bleach effect: test fabrics WFK CFT BC-1, WFK CFT BC-4, WFK CFT CS-3

Enzyme effect: test fabrics EMPA 112, EMPA 116, WFK CFT AS-10

Inorganic incrustations: test fabrics EMPA cotton, Vossen terry towel, WFK 10A, WFK 16A, WFK 20A

Sodium percarbonate is used as a bleaching agent in modern detergents. The storage stability of unprotected percarbonate does however suffer – even if atmospheric moisture is excluded – if it comes into contact with aqueous substances. SKS-6 is anhydrous and gives advantages in storage stability because it does not intro- duce any additional stability- reducing water into the detergent. If type A zeolite is used together with SKS-6 and sodium percar- bonate, specially coated percarbonate should be used.

Using mathematical methods it is possible to put the results of washing tests into a mathematical model. In the course of a study, formulations for compact detergents were systematically varied and the influence was determined of the builder/cobuilder system on wash effect, bleach effect, enzyme effect and inorganic incrustations. The main builder SKS-6 and zeolite formed the varied components, polycarboxylate was used as cobuilder and bicarbonate as pH control. The other components such as surfactant system, bleaching system and additives were not varied (Fig. 57).

fIgure 57: Model wash test formulas

 

[%]

SKS-6 powder*

0-40

zeolite a

0-40

Bicarbonate

0-15

Polycarboxylate

0-6

Percarbonate 15, genapol oa 080* 8, anionic 6, citric acid 6, Peractive an* 3, enzyme 2.5, anti- foam 1, Soap 1, opt. brightener 0.5, Perfume 0.5, Phosphonate 0.5, Sulphate to 100 %

* Clariant product brand names

fIgure 58: Wash effect, bleach effect, enzyme effect and inorganic incrustations in model wash test

1.2

0.6

0

-0.6

-1.2

SKS-6

Wash effect Bleach effect Enzyme effect Inorganic incrustations n Polycarboxylate n Zeolite n Bicarbonate
Wash effect
Bleach effect
Enzyme effect
Inorganic
incrustations
n Polycarboxylate
n Zeolite
n Bicarbonate

The mathematical model then evaluates the different results and interprets increasing or decreasing influences as coefficients. The detergency was, as is usual, determined as delta remission of the soiled fabrics prior to and after one wash. The resulting coefficients were standardised.

As a supplier of alkalinity, SKS-6 increases detergency (Fig. 58). Because of its chelating and soil dispersing properties the poly- carboxylate also increases detergency. As zeolite only functions as a water softener it cannot support the effect of the surfactant system. Bicarbonate, which lowers the pH, reduced the detergency. The influence of builder and cobuilder on the efficacy of enzymes is somehow similar to the influence of the builder on the surfactants. Whereas SKS-6 and polycarboxylate increase the enzyme effect, zeolite and bicarbonate weaken it.

SKS-6 boosts the bleaching effect. The positive effect can be due as much to effective pH buffering as to stabilisation of the bleach sys- tem. The chelating properties of the polycarboxylate can reinforce bleaching in two ways. Firstly, as it leaches alkaline earths it gives peroxide molecules access to bleachable soil and secondly, it keeps heavy metal traces masked in solution, thus avoiding their adverse effects.

The inorganic incrustations were determined after 25 wash cycles as ash content. While SKS-6 helps to reduce incrustation, zeolite results in noticeably higher ash values. As is shown in earlier analyt- ical investigations of incrustations, the effect of zeolite is not to be attributed to insufficient softening of the water but probably to an insufficient dispersion of the zeolite. Polycarboxylates do their job and reduce the inorganic incrustations. As expected bicarbonate, because of its high carbonate ion content, demonstrates a noticeable influence that tends to result in higher ash values.

Compact detergents

Since the multifunctional builder SKS-6 combines various func- tions, new formulations for highly compact detergents can be produced. SKS-6 can be used as a stand-alone builder or combined with others, e.g. with zeolite or phosphate. Builder mixtures of SKS-6 and Zeolite A exhibit an optimised price/performance ratio. SKS-6 can be processed by the modern mixing methods for deter- gent production. It can be used as a carrier for liquid components, e.g. surfactants.

Suggestions for formulations of heavy-duty powder detergents with SKS-6 are given (Fig. 59). The formulations differ in compactness and dosage in the wash cycle.

Formulation 1 based on SKS-6 is technologically easy to manu- facture as SKS-6 facilitates incorporation of the surfactants. The other components are mixed in. Only readily biodegradable surfactants are used and polycarboxylate can be omitted. Both are ecologically beneficial measures. Percarbonate can be used as a bleach and does not need to be protected against attack by water. Being based solely on easily dispersable components, this formula- tion meets the requirements of modern detergents.

Formulation 2 is based on SKS-6 and type A zeolite in equal amounts. Citric acid and soda/bicarbonate supplement the builder block. Polycarboxylates are used for dispersion. Because of the zeolite component it is advisable to employ coated sodium percar- bonate. Formulations 1 and 2 are aimed at low dosage, compactness and very high detergent performance.

Formulation 3 is a low-cost alternative, in which a higher amount of zeolite is used and citric acid is omitted. The higher zeolite content requires a higher addition of polycarboxylate.

Model washing tests show that all formulations give satisfactory results with regard to inorganic incrustations and well-balanced detergency as well as bleaching effect (Fig. 60).

fIgure 59: SKS-6 based compact and supercompact detergent formulas

 

1 [%]

2 [%]

3 [%]

SKS-6 granular*

48

15

15

zeolIte a

15

30

SoDa or BIcarBonate

15

12

13

cItrIc acID

6

PerBorate · h 2 o

15

PercarBonate

15

20

PeractIve an*

5

5

6

PhoSPhonate

0.5

0.5

0.5

anIonIc

8

6

genaPol oa 080*

10

9

4

PolycarBoxylate

4.5

6

enzymeS

2.5

2.5

2.5

oPtIcal BrIghtener

0.5

0.5

0.5

Perfume

0.5

0.5

0.5

antIfoam

1

1

1

SulPhate

to 100

to 100

DoSage g/waSh

60

60

75

* Clariant product brand names

teSt conDItIonS

Miele W 917, main wash programme, 60 °C, 18 °d, 15 wash cycles

Wash effect: test fabrics WFK 10C, WFK 10D, WFK 20D

Bleach effect: test fabrics WFK CFT BC-1, WFK CFT BC-4, WFK CFT CS-3

Inorganic incrustations: test fabrics EMPA cotton, WFK 20A

Formulation 1, which contains only SKS-6 as builder, is particularly efficient. Formulations 2 and 3

Formulation 1, which contains only SKS-6 as builder, is particularly efficient. Formulations 2 and 3 with zeolite/SKS-6 combinations also show very good washing results with all fabrics and types of soil. The modern formulation 2 containing citric acid, boosted by a higher surfactant content, has the same primary washing effect as formulation 3, which is richer in zeolite, but higher in dosage.

All formulations have roughly the same bleaching performance.

Studies of inorganic fabric incrustations after 15 washes show that the secondary detergent power of all SKS-6 formulations meets the current standard. The SKS-6 stand-alone formulation 1 does this without the addition of polycarboxylate. To obtain comparable ash values it is necessary to add polymers to the formulations containing zeolite. Polycarboxylates as dispersing agents have a very marked influence on the secondary washing effect.

A high measure of performance and multifunctionality is also realised in two other formulations (Fig. 61).

Formulation 4 – like formulation 1 – uses SKS-6 in combination with sodium bicarbonate as builder system. Percarbonate and bleach activator TAED (e.g. Peractive AN) are used for the bleach- ing process. This lies in the general trend towards lower washing temperatures. The surfactant system is composed exclusively of nonionic surfactants and no polymers are used for soil dispersion. As is generally practised, enzymes, foam regulators, optical brighteners and fragrance are included in the formulation.

fIgure 60: Wash effect, bleach effect and inorganic incrustations of SKS-6 based compact detergent formulas

30 3 20 2 10 1 1 SKS-6 2 SKS-6 + Zeolite 3 SKS-6 +
30
3
20
2
10
1
1 SKS-6
2 SKS-6
+ Zeolite
3 SKS-6
+ Zeolite 1 : 2
A Wash effect
n B Bleach effect n C Inorganic incrustations
fIgure 61: SKS-6 based compact detergent formulas
4 [%]
5 [%]
SKS-6 granular*
45
15
zeolIte a
15
SoDa
3.8
BIcarBonate
11.7
cItrIc acID
6.2
PercarBonate
20
25
PeractIve an*
5
5
anIonIc
8
genaPol oa 080*
10
9
PolycarBoxylate
4.5
enzymeS
4
4
otherS
4.3
4.5
* Clariant product brand names
A, B delta R [%]
C Ash [%]

teSt conDItIonS

Single wash cycle, wash and wear test, 60 °C, approx. 14 °d, dosage 72 g/wash

Degree of whiteness: 15 wash cycles, averages of 3 fabric types

Stain removal: averages of 13 stain types, each 1 cycle, 5 repetitions

Inorganic incrustations: standard cotton fabric, 15 wash cycles

Ash [%]

A builder system comprising SKS-6, zeolite A, soda ash and citric

acid is used in formulation 5. The bleaching system is made up of

percarbonate and Peractive and the surfactant system comprises anionic and nonionic surfactants. Because of the zeolite content, polymers are used for dispersing. The same other additives that are used in formulation 1 complete this formulation.

In a wash-and-wear test in an independent test institute, the degree

of whiteness (according to Ganz/Griesser), stain removal (here

the fabrics were visually checked and the stain removal graded) and inorganic incrustations (ash) were tested on specific test fabrics. In all three tests these test detergents achieved the same performance level as leading detergent brands (Fig. 62).

The use of SKS-6 HD in heavy-duty detergents was tested in model washing tests (Fig. 63).

Formulation 6 serves as comparison and contains a combination of SKS-6, zeolite A and polycarboxylate.

In formulation 7 SKS-6 HD, SKS-6 and zeolite were used. It contains so much SKS-6 HD that a polymer content of 4 % results.

Formulation 8 contains a mixture of SKS-6 HD and SKS-6, which results in an SKS-6 content of 40 % and a polymer content of 4 %. In total this is a lesser polymer content than is usual for example with zeolite formulations. The remaining components – comprising anionic and nonionic surfactants, percarbonate, Peractive, enzyme and antifoaming agent – were kept constant, and sulphate made up the remainder of the 100 %.

Finally the formation of inorganic incrustations was investigated (Fig. 64). Normally these increase in the course of repeated washing. It is apparent that the zeolite-containing formulation without SKS-6 HD results in the most incrustations. The ternary system SKS-6/SKS-6 HD/zeolite is more advantageous (i.e. less incrustations than with the above), the best results are obtained with the formulation combining SKS-6 HD and SKS-6.

teSt conDItIonS

Miele W 917, main wash programme, 60 °C, 18 °d, dosage 75 g/wash

Inorganic incrustations: after 25 wash cycles, test fabric Vossen terry towel

fIgure 62: Degree of whiteness, stain removal and inorganic incrustations of SKS-6 based compact detergent formulas

100 4 90 2 80 0 4 SKS-6 5 SKS-6 + Zeolite A Degree of
100
4
90
2
80
0
4 SKS-6
5 SKS-6 + Zeolite
A Degree of whiteness (Ganz/Griesser)
n B Stain removal
n C Inorganic incrustations
fIgure 63: SKS-6 HD based compact detergent formulas
6 [%]
7 [%]
8 [%]
SKS-6 PowDer*
20
7.3
27.3
SKS-6 hD*
18.2
18.2
zeolIte a
25
25
PolycarBoxylate
4
A [%]
B [Scores], C Ash [%]

PercarBonate 20, anIonIc 9, genaPol oa 080* 8, PeractIve an* 5, enzyme 2, antIfoam 1, Sulfate to 100 %

* Clariant product brand names

fIgure 64: Inorganic incrustations of SKS-6 HD based compact detergent formulas

2.5

1.5

0.5

6 SKS-6 + Zeolite

7 SKS-6 + SKS-6 HD + Zeolite

8 SKS-6 + SKS-6 HD

Laundry tablets

Laundry tablets DISIntegratIon teSt conDItIonS 30 °C, 15 °d, 950 ml water, tablet in sieve basket with mesh size

DISIntegratIon teSt conDItIonS

30 °C, 15 °d, 950 ml water, tablet in sieve basket with mesh size 5 mm

Wash test conditions: main wash programme, 60 °C, 18 °d, dosage: 2 tabs 40 g each via drawer dispenser, 15 wash cycles

Wash effect: test fabrics EMPA 104, WFK 10C, WFK 10D, WFK 20D

Bleach effect: test fabrics WFK CFT BC-1, WFK CFT BC-4, WFK CS-3

Inorganic incrustations: test fabrics EMPA cotton, Vossen terry towel, WFK 10A, WFK 16A, WFK 20A

The formulations for laundry tablets are similar to those for deter- gent powders. To solve the specific problems of tablet shape and the higher density and the resulting more difficult decomposition on introduction into the wash liquor, basically three types of »tabs« have evolved. The first type uses phosphate as an easily soluble builder. The second type is phosphate free, only slightly compacted, coated with a layer of e.g. fatty acid which stabilises the shape, and laced with bicarbonate and citric acid to give an effervescent effect. Type 3 is compacted sufficiently to keep its shape, and contains a disintegrant, e.g. cellulose, microcrystalline cellulose, polyacrylic acid and other ingredients. Dissolving agents in the form of easily soluble salts are also utilised.

SKS-6 can of course be used together with different disintegrants or dissolving agents. Formulation 1 is based on cellulose as disinte- gration additive. Formulation 2 for example can be considered a basic formulation using easily soluble salts as disintegrant (Fig. 65). In a model wash test, (Fig. 66) formulation 1 is shown to have good disintegration properties, good detergency and low tendency to form inorganic incrustations.

fIgure 65: SKS-6 based laundry tablet formulas

 

1 [%]

2 [%]

SKS-6 granular*

20

10

zeolIte a

10

15

SoDa

13

12

anIonIcS

10

8

nonIonIc

7

7

celluloSe

5

acetate · 3 h 2 o

10

PercarBonate 15, cItrIc acID 5, PolycarBoxylate 4, PeractIve an* 4, aDDItIveS anD SulPhate to 100 %

* Clariant product brand names

 

fIgure 66: Disintegration, wash effect, bleach effect and inorganic incrustations of SKS-6 based laundry detergent tablet formulas

40 4 20 2 0 0 A [s]; B, C delta R [%] D Ash
40
4
20
2
0
0
A [s]; B, C delta R [%]
D Ash [%]

1 SKS-6

A Disintegration n B Wash effect

Commercial premium brand

n C Bleach effect n D Inorganic incrustations

Regular detergents

Formulations 1 to 3 (Fig. 67) are similar to current conventional ones. Sodium perborate tetrahydrate is used in all cases as oxygen donor. A corresponding amount of sodium sulphate is used to achieve the recommended dosage. The contents of sodium car- bonate and sodium sulphate can be substituted for each other within certain limits.

The third standard formulation is designed for all regions where phosphate is used as detergent builder. The polycarboxylate content is reduced and TAED is omitted.

The individual components of the detergent formulations are listed here as general substance designations. The sequence follows from the context and does not correspond to a manufacturing specification. We will gladly answer your questions on manufactur- ing specifications and precise grade designations.

The efficiency of the formulations is indicated below by means of washing tests in which the detergent action on washable and bleachable soil and the tendency towards inorganic incrustation was tested (Fig. 68).

Both phosphate free formulations have roughly the same washing results and bleaching performance. In the formulation containing phosphate the addition of TAED is omitted, and therefore the bleaching efficiency is somewhat lower.

Formulation 2 also demonstrates clearly that polycarboxylates have to be used with detergent formulations containing zeolite to obtain acceptable incrustation values. Formulation 3, which contains phosphate, naturally shows the best secondary detergent power of all the detergent formulations.

teSt conDItIonS

Miele W 917, main wash programme, 60 °C, 18 °d, dosage 135 g/wash, 15 wash cycles

Wash effect: test fabrics WFK 10C, WFK 10D, WFK 20D

Bleach effect: test fabrics WFK CFT BC-1, WFK CFT BC-4, WFK CFT CS-3

Inorganic incrustations: test fabrics EMPA cotton, WFK 16A

fIgure 67: SKS-6 based regular detergent formulas

 

1 [%]

2 [%]

3 [%]

SKS-6 PowDer*

21.3

8.3

7.4

zeolIte a

8.3

SoDIum trIPolyPhoSPhate

22.2

SoDa or BIcarBonate

6.7

6.7

PerBorate · 4 h 2 o

25

25

25

PeractIve an*

2.2

2.5

PhoSPhonate

0.2

0.3

0.2

anIonIcS

4.4

6.7

genaPol oa 080*

4.4

5

2.2

PolycarBoxylate

2.5

1.5

enzyme

1.1

1.4

1.4

oPtIcal BrIghtener

0.2

0.3

0.3

Perfume

0.2

0.3

0.3

antIfoam

0.4

0.6

0.6

SulPhate

to 100

to 100

to 100

* Clariant product brand names

Another formulation demonstrates the further use of SKS-6 HD with zeolite (Fig. 69). The polymer compound makes the addition of other polymers unnecessary and it can serve as carrier base for the nonionic surfactants. Test washing shows good detergency, good bleaching effect and a low tendency to incrustations (Fig. 70). Of interest is also the high compatibility with enzymes, as is demon- strated by their good washing results.

teSt conDItIonS Miele Novotronic 927 WPS, main wash programme, 60 °C, 18 °d, dosage 150 g/wash, 15 wash

teSt conDItIonS

Miele Novotronic 927 WPS, main wash programme, 60 °C, 18 °d, dosage 150 g/wash, 15 wash cycles

Wash effect: test fabrics: EMPA 104, WFK 10C, WFK 10D, WFK 20D, WFK 30D

Bleach effect: test fabrics: WFK CFT BC-1, WFK CFT BC-4, WFK CFT CS-3

Enzyme effect: test fabrics: EMPA 112, EMPA 116, WFK CFT AS-10

Inorganic incrustations: test fabrics: EMPA cotton, Vossen terry towel, WFK 10A, WFK 16A, WFK 20A

fIgure 68: Wash effect, bleach effect and inorganic incrustations of SKS-6 based regular detergent formulas

30 3 20 2 10 1 1 SKS-6 2 SKS-6 + Zeolite 3 SKS-6 +
30
3
20
2
10
1
1 SKS-6
2 SKS-6
+ Zeolite
3 SKS-6
+ Sodium tripoly-
phosphate
A Wash effect
n B Bleach effect
n C Inorganic incrustations
A, B delta R [%]
C Ash [%]

fIgure 69: SKS-6 HD based regular detergent formula

 

4 [%]

SKS-6 hD*

8

zeolite a

12

SoDa

15

PerBorate · 4h 2 o

20

PeractIve an*

2

anIonIc

7

genaPol oa 080*

5

antIfoam

0.4

enzymeS

1.4

SulPhate

29.2

* Clariant product brand names

fIgure 70: Wash effect, bleach effect, enzyme effect and inorganic incrustations of SKS-6 HD based regular detergent formula

40 4 30 3 20 2 10 1 A, B, C delta R [%] D
40
4
30
3
20
2
10
1
A, B, C delta R [%]
D Ash [%]

A Wash effect n B Bleach effect

1 SKS-6 HD + Zeolite

n C Enzyme effect n D Inorganic incrustations

Color detergents

Color detergents are supposed to be the gentle-on-color alternative to heavy-duty detergents. Color detergents are used wherever it is not necessary to remove stains and heavy soiling.

it is not necessary to remove stains and heavy soiling. These detergents for colored textiles therefore

These detergents for colored textiles therefore do not contain a bleaching system, instead, they contain a special color protection in the form of poly vinyl pyrrolidone and poly-4-vinyl pyridine-N- oxide as dye-transfer inhibitors and soil-release polymer for easier soil removal on union fabric. With enzymes often cellulase is uti- lised as an agent against felting and as softener and color improver, because it removes the diffuse discolored fibre surfaces and reveals the brilliant original color. Generally color detergents are used in the same dosage as heavy-duty detergents.

SKS-6 and SKS-6 HD are also particularly suitable for these special detergents (Fig. 71). SKS-6 is then used to advantage together with zeolite and citrate. SKS-6 HD simplifies the use of polymer and can serve as carrier for special surfactants. In a practice test (Fig. 72) these formulations are shown to have low incrustations, good deter- gency and a low adverse effect on the effectiveness of enzymes.

teSt conDItIonS

Miele Novotronic 927 WPS, main wash cycle, 60 °C, 18 °d, dosage 65 g/wash, 15 wash cycles

Wash effect: test fabrics EMPA 104, WFK 10C, WFK 10D, WFK 30D

Enzyme effect: test fabrics EMPA 112, EMPA 116, WFK CFT AS-10

Inorganic incrustations: test fabrics EMPA cotton, Vossen terry towel, WFK 10A, WFK 16A, WFK 20A

fIgure 71: SKS-6 based color detergent formulas

 

1 [%]

2 [%]

SKS-6 granular*

10

17

SKS-6 hD*

25

zeolIte a

33

cItrate

9

2

PolycarBoxylate

7

SoDa

12

BIcarBonate

8

Soap

2

1.5

genaPol oa 080* 10, anIonIc 8, Poly vInyl PyrrolIDone 3, enzymeS 2, antIfoam 1, SoIl-releaSe Polymer 1, carBoxymethyl- celluloSe 1, SulPhate to 100%

* Clariant product brand names

 

fIgure 72: Wash effect, enzyme effect and inorganic incrustations of SKS-6 and SKS-6 HD based color detergent formulas

30 3 20 2 10 1 0 0 1 SKS-6 2 SKS-6 + SKS-6 HD
30
3
20
2
10
1
0
0
1 SKS-6
2 SKS-6 + SKS-6 HD
A Wash effect
n B Enzyme effect
n C Inorganic incrustations
A, B delta R [%]
C Ash [%]

Fine-fabric detergents and water softeners

Fine-fabric detergents and water softeners Fine-fabric detergents are used for domestic washing of delicate fabrics such

Fine-fabric detergents are used for domestic washing of delicate fabrics such as wool. They are therefore of low alkalinity and con- tain special surfactants and additives for protecting fibres and colors. As alkalinity has an adverse effect on fine fabrics, it must not be too high. Therefore, a lower amount of SKS-6 is general- ly used. If preferred SKS-6 HD can also be used. Fig. 73 gives guide formulations for special detergents with SKS-6 and SKS-6 HD.

Especially in regions with very hard water, water softeners are important complements to heavy-duty detergents.

During the washing process a softener can be added to the deter- gent, this helps to counter the formation of deposits and incrusta- tions on heating coils and internal surfaces of washing machines. In accordance with this main task, water softeners are principally made up of builder and cobuilder components (Fig. 74). Here too, SKS-6 acts as alkali supplier and water softener in one. Above all it protects effectively against the deposits of mixtures from calcium carbonate and magnesium carbonate. Standard formulations also contain zeolite for removing calcium, soda as alkali supplier and to increase cleansing, polycarboxylate to disperse soil and to soften water immediately at the beginning of the washing cycle. Small amounts of nonionic surfactants may also be included as required.

fIgure 73: SKS-6 based fine-fabric detergents

 

1 [%]

2 [%]

3 [%]

4 [%]

5

[%]

SKS-6 granular*

5

12

3

 

SKS-6 hD*

25

 

15

zeolIte a

20-25

12

 

10

SoDIum trIPoly-

25

 

PhoSPhate

 

cItrIc acID

6

3

 

3

laS/faS

15

15

15

15

 

15

genaPol oa 080*

3

3

3

3

 

3

SoaP

1-3

1-3

1-3

1-3

 

1-3

PolycarBoxylate

2-3

3

1

 

carBoxymethyl-

1

1

 

1

celluloSe

 

PhoSPhonate

1

1

 

1

Poly vInyl PyrrolIDon

1

1

 

SulPhate

to 100

to 100

to 100

to 100

to 100

*

Clariant product brand names

fIgure 74: SKS-6 based water softener formulas

 

6 [%]

7

[%]

SKS-6 granular*

10-40

 

SKS-6 hD*

 

15-50

zeolIte a

20-60

 

20-60

SoDa or BIcarBonate

0-20

 

0-20

PolycarBoxylate

5-15

 

cItrate

0-40

 

0-40

SulPhate

0-30

 

0-30

Surfactant

0-5

 

0-5

*

Clariant product brand names

 

SKS-6

automatIc DIShwaSher DetergentS

53

Automatic dishwashing detergents

Modern dishwashing detergents are balanced blends of various components: builder, cobuilder, alkalis, oxidising agents, enzymes, surfactants, bleach activators, fillers, and, if required, fragrance. Their interaction in the dishwashing machine is the prerequisite for transforming used dirty dishes into clean and hygienic dishes with the least possible use of energy and water while being as gentle on the items in the dishwasher as possible.

The most important tasks of a dishwashing detergent are the removal of soil from the items in the dishwasher, dispersion of the soil in the liquor and the chelating of residual water hardness and hardness ions from food residues in order to prevent deposits on the items in the dishwasher and on the dishwasher interior. In addition to this it must also have foam-regulating properties, so as not to impair the cleaning effect of the dishwasher liquid.

Today, however, the excellent cleaning effect of a dishwashing detergent no longer is enough for it to be called an optimum deter- gent. In addition to this it must prevent corrosion on the items in the dishwasher. This includes glass corrosion or tarnishing of silver cutlery.

Today dishwashing detergents are offered in phosphate containing and phosphate free formulations, either as solids or liquids. They are used most frequently in the form of tablets and granules; particularly tablets ensure easy use and represent the ideal form of a compact cleaner.

Liquid dishwashing detergents, despite a lower concentration of the materials have the advantage that they are already in liquid form and can become effective as soon as they have been added to the dishwasher liquor.

SKS-6 and SKS-6 HD are the preferred raw materials for this application.

HD are the preferred raw materials for this application. fIgure 75: SKS-6 based phosphate free automatic

fIgure 75: SKS-6 based phosphate free automatic dishwashing detergents

 

1 [%]

2 [%]

3

[%]