ANTISPUMIN ®

Defoamers and Deaerators

Ashland Deutschland GmbH
Ashland Water Technologies
Fütingsweg 20, D-47805 Krefeld
P.O. Box 10 04 52, D-47704 Krefeld
Phone: +49 2151 38 3052
Fax: +49 2151 38 1106
water@[Link]
[Link]

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Contents Page

1. Introduction 4

2. Foam Formation 7
2.1 Gibbs´ Elastic Films and the Marangoni Effect 12
2.2 Rheological Aspects of Foam Stability 12
3. Defoamers 14
3.1 Oil and Fat Defoamers 14
3.2 Polyalkylene Glycols 14
3.3 Defoamers Consisting of Oils and Hydrophobic Particles 15
3.3.1 Particle Geometry 15
3.3.2 Capturing the Particles with Air Bubbles and Fusing the Particles 16
3.3.3 Mechanism of Action of Hydrophobic Particles in Oils 16
3.4 Mechanism of Action of Deaerating Agents 17
3.5 Composition of Defoaming and Deaerating Agents 18
3.6 Recommended Fields of Application for ANTISPUMIN Defoaming
®

and Deaerating Agents 20

4. Testing of Defoaming and Deaerating Agents in the Laboratory 21

4.1 General Selection Criteria for Defoaming and Deaerating Agents 21
4.2 Laboratory Tests with ANTISPUMIN® Defoaming and
Deaerating Agents 21
4.2.1 Shaking Method 22
4.2.2 Perforated Disc Impact Method 23
4.2.3 Stirring Method 24
4.2.4 Pump Circulation Method 25
4.2.5 Air (or Gas) Injection Method 26
4.2.6 Special Test Methods 26

5. Defoaming Agents for Food and Animal Feed 27

6. Solution for your Foam Problems 27

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ANTISPUMIN ®

Defoamers and Deaerators

1. Introduction

Apart from a few exceptions such as removing ink from used paper and in the flotation of ores
and minerals, foams are generally undesirable. Foams disturb production sequences in which
liquids, particularly water, have an important function as transporting media or solvents, and in
the worst cases they can even bring such processes to a standstill. Furthermore, foams can lead
to lower production yields and finished products of poorer quality.

Some examples to illustrate this are given below:

During sugar production from sugar beet, considerable problems due to foam occur Sugar production from
in the entire inside and outside working areas. sugar beet

Fig. 1: Foam in a sugar factory

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 Many effluents from the chemico-technical industries as well as the paper and cellulose
industry cause considerable environmental problems due to foam formation.
Entrapped air bubbles in the pulp used for paper manufacture can cause Pulp used for paper
breaking down of the sheet. Air containing material necessitates increased pump work manufacture
when conveying the material. In addition, defects are produced in the paper resulting
from foam bubbles.
Entrapped air bubbles in dyes used in the paper industry lead to defects in the coating, Dyes used in the paper
and therefore to a reduction in quality. This leads to complaints by the user of such industry
coated paper.
Foam is undesirable in the production of dispersion paints. Foam causes a reduction in Production of dispersion
capacity of the mixing vessel and the formation of “craters” during application of the paints
dispersion paint.
In biotechnical processes, e. g. during the production of penicillin, enzymes, yeast, Biotechnical processes
citric acid and glutamic acid, foam causes difficulties in controlling the reaction and
results in a reduction in the yield.
In the wet attack of phosphate rock with sulphuric acid, foam production can cause a Wet attack of
reduction in the capacity of the reactor, a decrease in the pump output and to phosphate rock with
difficulties in the filtration stage. Furthermore, considerable problems are likely in the sulphuric acid
evaporation stages.
Foam on lubricant emulsions in metal working leads to an insufficient cooling effect Lubricant emulsions
and thus to overheating of the cutting tools.
Foam formed on drawing oil emulsions during the drawing of non-ferrous metal wires Drawing oil emulsions
leads to an inadequate cooling effect. This results in hot running of the drawing dies
and therefore premature wear and breaking of the wire in extreme cases.

Fig. 2: Foam in a sewage plant

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 In mining, flotation foam causes difficulties in the thickening of concentrates and in de- Mining
watering. Residual quantities of flotation reagents in the flotation tailings lead to
problems with clarification.
Effluents in industrial and local authority sewage plants contain a number of different Mechanical and biological
foam-forming substances. In mechanical and biological sewage plants foam causes sewage plants
clarification problems and environmental pollution.

Foaming
Foaming is a physical process which leads to the formation of foam.
Foam
Foam is defined as the entirety of all cells separated by liquid lamella, that are formed
by an accumulation of bubbles. The liquid lamellae are very thin and often have a
thickness of between only a few nanometres and 10 µm.
Gas bubble
A gas bubble is a cavity or cell filled with gas, that is surrounded by a thin liquid
envelope.
Foaming capacity
Foaming capacity is the level of the ability to form a foam.
Foam stability
Foam stability is the degree of the ability of a foam to remain stable.
Foam dewatering
Foam dewatering is the return flow of excess liquid to the liquid phase. The excess
liquid is entrained by the gas bubbles during foaming.
Defoaming agent (anti-foaming agent, defoamer, foam removing oil)
A defoaming agent is a product which prevents the formation of (surface) foam, or
considerably decreases its stability and destroys it.
Deaerating agent
A deaerating agent is a product which causes rapid accumulation (enlargement) of the
gas bubbles dispersed in a liquid. This results in a considerably improved ability of the
air to escape from the liquid.

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2. Foam Formation

Pure water cannot form a stable foam, and even when a high mechanical force is applied, e. g.
by pumping and stirring, the air introduced still escapes very quickly. The spontaneous escape
of air bubbles from pure water is represented in figure 3.

Unstable,
that means
no foam

Air

Water

Fig. 3: Self-deaeration in pure water

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However, if the water contains special dissolved or also non-dissolved components, relatively
stable dispersions of air in water can be formed. The result then is the formation of foam on the
water surface (see figure 4).

Stable foam

Air

Water

Fig. 4: Self-deaeration of water with dissolved and non-dissolved components

The durability (life, stability) of the foam produced can vary greatly. Foams that break down
very quickly are not likely to cause problems. On the other hand, very stable foams may also
be formed, which in the most unfavourable cases may even dry without breaking down. How-
ever, foams are generally only formed if the water contains surface-active agents (surfactants,
proteins, cellulose derivatives, polyelectrolytes or polysaccharides).

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Surfactants are chemical compounds which are preferentially adsorbed on an interface when Surfactants
dissolved or dispersed in a liquid. The molecules of the tenside surfactants have a hydropho-
bic (= lipophilic, i. e. water repellent = oil attracting) organic residual part, and a hydrophilic
(= lipophobic, i. e. water attracting = oil repellent) group (see figure 5).

Hydrophobic organic residual part

Hydrophilic group

Fig. 5: Graphic representation of a surfactant molecule

The surfactant molecules settle on the water/air interface in such a way that the hydrophilic part Water/air interface
of the molecule is in the water, and the hydrophobic part in the air. A monomolecular layer is
formed – i. e. a thin film – from the surfactant molecules (see figure 6). Formation of a
monomolecular layer

Air

Water/air inter-
face

Water

Surfactant
molecule

Fig. 6: Formation of a monomolecular layer of surfactant molecules

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This layer (film) is the precondition for the formation of stable foams. The high concentration
at the water/air interface means that frequently only very small quantities of surfactant (foam-
ing agent) in relation to the total quantity of water are sufficient to bring about considerable
foam formation.

First of all, the small air bubbles dispersed in water have a spherical shape. When these small When no surfactants are
air bubbles rise to the water surface and no surfactant is present, a spherical foam is formed, present: spherical foam
which breaks down very rapidly through bubble growth (see figure 7).

Fig. 7: Spherical foam

If, however, surfactants are dissolved in the water, the monomolecular elastic layer which is
formed at the water/air interface is raised by means of the escaping gas bubbles and surrounds
the foam bubble on the outside. A corresponding layer is likewise formed on the inside of the
foam lamella, and in this case the hydrophobic residual parts of the surfactant molecule also
project from the water (see figure 8).

Air

Monomolecu-
lar layers of
surfactant mol- Water
ecules

Air

Fig. 8: Schematic section of a foam lamella

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Foam that has been stabilized by a surfactant is only slowly dewatered, since the water only
flows off gradually under the influence of gravity and the foam lamella becomes thinner and
more unstable. Like electrical charges may also contribute to the stability of the foam lamella,
i. e. when the foam lamella becomes thinner the surface layers with the same charge repel.
Furthermore, draining of the water between the surface layers is slowed down further due
to the strong bond of the water to the hydrophilic groups of the surfactant. The stable foam Dissolved surfactant:
bubbles then coalesce to larger bubbles, and in doing so they lose their spherical shape and a polyhedral foam
polyhedral foam is formed (see figure 9).

Fig. 9: Polyhedral foam

Until the maximum spreading pressure is reached additional surfactant molecules are taken up Foam production
by the layer and a two-dimensional structure is produced. The critical micelle concentration
is thereby reached and the spreading pressure remains constant.

There are several methods of foam production:

1. Dispersion method: enlargement of the surface regions between the liquid and the
gas by mechanical action (stirring, pumping)
2. Condensation method: production of gas bubbles from a supersaturated solution of
the gas (beer or CO2 -containing solutions)
3. The finely distributed introduction of gas into a medium (biological stage of effluent
treatment)

Foam stabilisation is explained by two related effects.

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2.1 Gibbs´ Elastic Films and the Marangoni Effect

Gibbs Film Elasticity

As the lamella expands the surfactant concentration is reduced locally, resulting in an Gibbs
increase in surface tension. The high surface tension creates a restoring force which
stabilises the foam (Gibbs).
Marangoni Effect
As the lamella expands the water flows back more quickly than the surfactant mol- Marangoni
ecules. The water that is flowing back increases the layer thickness of the lamella and
thereby stabilises the foam.

In the case of foam bubbles such local expansion occurs frequently. To this extent both effects
are necessary for stabilisation.

Due to the loss of liquid in the lamellae the wet foam turns into a dry one. The plateau zones
absorb liquid, whereby the lamellae can become so thin that they affect one another.

Van der Waals forces, electrostatic and steric forces counteract this destabilisation. The van
der Waals forces cause the two surfaces of the lamella to attract one another, so that more
liquid is squeezed out. However, if the liquid contains dissolved ions which can form an
electric charge layer (surfactants), the repulsion of the like charge results in stabilisation of
the thin lamellae.

Similarly, dissolved macromolecular stabilisers (e. g., polyelectrolytes, proteins, saponin) can
lead to mutual repulsion of the lamella surfaces through steric obstruction.

2.2 Rheological Aspects of Foam Stability

Lamella lose liquid under the influence of gravity. This reduces their stability. They are sta- Slightly increased
bilised by all forces that minimise the efflux of liquid. A slight increase in viscosity in the viscosity stabilises
interlaminar liquid stabilises the foam, while viscosities that are too high can prevent foam foam
formation.

Surface Shear Viscosity

A high surface shear viscosity should also stabilise the foam. This occurs, for example, through
the addition of higher alcohols or other water-insoluble substances. If the surface shear velocity
is low the foam decomposes more quickly.

The foam can also be located in a finely dispersed state between solids. Such foams can be
very firm and can form a stable surface when they dry out, as is also observed in the case of
floating sludge in the biological cleaning stage.

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Apart from surfactants, there are also high molecular organic compounds which can accumu- High molecular organic
late at the water/air interface. These include, for example: compounds

Saponins (in sugar beet etc.)

Proteins (e. g. gelatine, casein and albumin)
Polysaccharides (e. g. starch, pectins and hemi-cellulose)
Cellulose derivatives (e. g. cellulose ethers and carboxy methyl cellulose)
Humic acids
Polyelectrolytes

In some cases extremely high stabilization of foams which have been formed can be produced by Possible consequence:
these substances. These obstinate, stable and elastic foams are so-called micro bubble foams. micro bubble foam
Apart from the dissolved substances mentioned, under certain conditions a foam can also be
stabilized by finely distributed solids, which are concentrated on the surface of the foam bubbles,
such as fibre fragments (e. g. cellulose, synthetic plastic and mineral fibres), pigments (and fill-
ers), calcium soaps and metallic hydroxides. In some cases, for example in paper mills and
sewage plants, any foam that is formed visibly on the surface of the aqueous phase indicates at “Invisible foam”
the same time the presence of an “invisible foam,” i. e. the dispersed air in the aqueous phase. = dispersed air

On the other hand, aqueous phases containing solids (suspensions) can contain considerable
quantities of air, without any significant surface foam being formed. Although there are es-
sentially the same substances that promote the formation of surface foam and increase the air
content of the suspension, the mechanism is different.

The air content depends to a considerable extent on the interaction between the solids surface and Air content
dispersed air. The small air bubbles (diameter in the range 10 - 100 µm) may be retained or
rejected, depending on the charge of the solids surface. Since this charge depends on the pH-
value and the electrolytes dissolved in the water, the air content is also affected by these factors.
Substances which produce a hydrophobic effect on the solids surface, e. g. resins, can also
increase the air content. Figure 10 shows an enlarged section of a suspension containing air.

Fig. 10: Solid suspension containing air (paper industry)

The dispersed air often also causes undesirable flotation of the solid particles.

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3. Defoamers

As the lamella becomes thinner it reaches a point at which boundary layer forces prevent a Mechanism of action
further reduction in the thickness of the wall. These forces may be electrostatic or steric and of defoamers
come from the surface-active substances which make the foam possible.

A defoamer must be present as undissolved particles or droplets in the medium that is to be

defoamed. In contrast to what was stated in many older publications, it has not been possible
to establish in more recent literature any connection between the effect of the defoamer and
the spreading of the oil on the water-air surface.

Often the mechanism of action is considered to be the replacement of the foaming substance in
the lamella by a spread film of a new substance, which can be equated with elimination of the
stabilising surface tension gradient. In some cases this mechanism does indeed appear to apply.
For example, the addition of octanol results in a very rapid reduction in surface tension.

However, analyses conducted up to now have not shown any connection between the reduction
in surface tension as a result of a spreading liquid in the lamella and the effect of the defoamer.
It has also not been possible to prove by experiment the creation of a surface tension gradient
through the spreading of the defoamer liquid. It is possible that the spreading liquid draws the
underlying liquid of the foam lamella along with it, with the result that this becomes thinner
and tears. This would create a kind of Marangoni spreading.

3.1 Oil and Fat Defoamers

Defoamers consist of oils, fats, polyalkylene glycols and emulsifiers and usually take the
form of a clear to slightly turbid oily liquid. When they are diluted with water, a low-stabil-
ity emulsion is produced. The resulting oil droplets have a defoaming effect in combination
with the polyalkylene glycols. Similar principles to those described under 3.3 apply to the
mechanism of action.

3.2 Polyalkylene Glycols

This group also includes the so-called EO-PO block polymers, the ethylene diamine EO-PO Polyalkylene glycol
block polymers, the polyalkylene glycols based on polyols and the fatty alcohol EO-PO es- ethers and esters
ters, as well as the fatty acid EO-PO esters. These are non-ionic, low-foam surfactants which are effective above the
have a defoaming effect in the vicinity of or above their cloud point. The cloud point is the cloud point
temperature range in which the surfactants become insoluble in water. Often it is not possible
to measure an exact cloud point in water because the solutions are already turbid in water at a
temperature of 10 – 20 °C and become even more turbid when the temperature is increased.

The process of becoming turbid is reversible, i. e. upon cooling down the solutions become
clear again, or at least clearer than they were. A polyalkylene glycol does not have a standard
molecular weight, which is why it is not possible to determine a specific cloud point. Some
molar weight fractions are soluble for longer, while others are soluble only for a shorter time.
As the cloud point can be influenced by other chemicals, all cloud point information should
only be seen as approximate values. This system is comparable with oil defoamers, as a mixture
of organic phase (droplets) and water is produced in the vicinity of the cloud point. In contrast,
the oil phase here consists of insoluble surfactant droplets however.

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Unlike the turbidity range in water, the analytically determined cloud point is a physicochemi-
cal variable used to characterise a surfactant. This cloud point is often measured in butylene
diglycol (BDG) or BDG-water mixtures, but its relevance to the effectiveness of a defoamer
in application technology is limited.

3.3 Defoamers Consisting of Oils and Hydrophobic Particles

The use of hydrophobic particles in oil defoamers based on mineral oils or silicone oils has Mechanism of action of
been described in the patent literature for a long time (1950), and the theme has also been oil defoamers with and
taken up in literature since 1970. It is generally known that oils or hydrophobic particles alone without hydrophobic
have only a slight defoaming effect with respect to anionic surfactants. When used together particles
their performance increases approximately sevenfold.

If solid particles are suspended at the liquid-liquid interface and belong to both interfaces,
they possess an angle of contact to both surfaces. For a good defoaming effect a low level of
wettability (high contact angle) is required. Therefore the air-water contact angle should be
more than 90°.

Hydrophobic particles that can be used are, for example, waxes, stearin, paraffins, metal
soaps and hydrophobised silicic acid. Quantities as small as 1 % hydrophobised silicic acid
in mineral oil are effective.

The above statements concerning the spreading behaviour of oils also apply in these oil-par-
ticle mixtures, although it is certain that the particles do not have any effect on the spreading
behaviour of the oils.

Although not proven experimentally, but possibly of decisive significance, is the formation of
oil lenses on the lamella. These form bridges which subsequently tear.

Also the theory that hydrophobic particles absorb surfactants from the lamella and transport
them to the water has been shown to be false.

In contrast, it has been shown beyond doubt that compounds form from oil droplets with
hydrophobic particles.

3.3.1 Particle Geometry

Particles with sharp corners and edges are more effective than round or smooth particles, as ex-
periments have shown. Precipitated particles often have an amorphous, undefined structure.

It has been shown that the film first has to become thinner and achieve approximately the di-
mensions of the particles. This process takes some time; the following film tear occurs within
<0.001 s. The smaller the particles, the longer the drying of the lamella takes until it reaches
the particle size. The smaller the particles, the more of them are contained in the medium for
a given dose, and the probability of a film tear increases.

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The thickness of the lamella lies approximately within the following orders of magnitude:

1 to 10 µm Interference colours Thickness of the

foam lamella
<0.1 µm Black films
approx. 0.05 µm Film tear

This means that even without the effect of the hydrophobic particles the film tears at 0.05
µm. Hydrophobic particles in defoamers should therefore be larger than 0.05 µm and smaller
than 1 µm.

In contrast, the defoaming properties of the products based on alkylene oxide adducts depend Alkylene oxide adducts
on the fact that at a certain temperature – the so-called cloud point – a second phase that is
richer in defoaming agents separates off. This process is induced by the higher solubility at
low temperatures and lower solubility at higher temperatures. This phase has a very destruc-
tive effect on the foam. However, the optimum level of foam destruction need not necessarily
lie at the temperature of the cloud point.

3.3.2 Capturing the Particles with Air Bubbles and Fusing the Particles

When the foam bubbles rise or are swirled up they can absorb hydrophobic particles from
the defoamer, which ultimately results in the disintegration of the bubble. Rough particles
and those with corners and edges are more likely to be captured than smooth particles. If one
considers oil-particle compounds, the role of the particles appears to consist in making pos-
sible the penetration of the oil droplets into the air-water surface.

Hydrophobic materials for defoamers often have melting points of less than 100 °C. It has
been shown that close to the melting point the defoaming effect of the particles is greatly
reduced.

The melting point/dissolving temperatures of the hydrophobic particles lie within the range
80 – 90 °C in the oil phase. It is of no significance whether the wax melts or is dissolved in
the oil.

Performance may be better shortly before the melting point because round particles have then
already been deformed by hydrodynamic forces. However, at this point performance may also
become worse in the case of angular particles.

3.3.3 Mechanism of Action of Hydrophobic Particles in Oils

No systematic analyses have so far been carried out on the influence of particle size on the Mechanism of action
effectiveness of oil-particle defoamers. However, if a partial mechanism is penetration into a
double layer between the oil droplets and air bubbles, the particle size should lie within the
same order of magnitude as the thickness of the lamella, e. g. >0.1 µm and <10 µm.

It can be assumed that oil droplets and hydrophobic particles form combined structures
(compounds) which initially settle on the foam lamella as a lens. Thereafter the compounds
penetrate to the other side of the lamella and form a bridge in the film. This film dries out in
exactly the same way as a film without hydrophobic particles. The drying out process is the
rate-determining step in the defoaming effect.

The film tear then occurs within a very short time.

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Observations of mineral oils and hydrophobic silicates indicate that improvements to defoamer
effectiveness for a given dosage are possible by reducing the size of the compounds to at least
1 – 2 µm.

3.4 Mechanism of Action of Deaerating Agents

Hydrophobic deaerating agent particles are embedded in the interface of the air bubbles dis-
persed in water, where they are drawn slightly to the centre of the bubble.

If a second air bubble now touches the embedded deaerating agent particle, disequilibrium
then results. The deaerating agent particle cannot take up its previous resting position, either in
the first or in the second bubble. The result is that the interface in the vicinity of the deaerating
agent particle is subjected to an increasing contact pressure, until both bubbles coalesce. The
bubble growth continues in this way. The upthrust of a bubble, which has been formed by the Rapid deaeration due
coalescence of two bubbles of about the same size, is double that of the original bubbles. This to bubble growth
results therefore in rapid deaeration.
Bubble growth is directly dependent on the number of bubble collisions per time unit. There-
fore a deaerating agent is also expected to achieve its optimum effect in turbulent zones.

Hydrophobic
Air bubble
Hydrophobic
deaerating agent particle
deaerating agent particle

Fig. 11: Mechanism of action of a deaerating agent

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3.5 Composition of Defoaming and Deaerating Agents

The following are important preconditions for the effectiveness of defoaming and deaerating
agents:

Lower surface tension than the medium to be defoamed (deaerated)

Low solubility in the medium to be treated
A sufficiently fine dispersion (formation of particle size with optimum effect)

Normally defoaming and deaerating agents should not react with the medium to be defoamed. Not all defoaming agents
There are a few exceptions to this rule, e. g. defoaming agents for the attack of phosphate rock are at the same time
with mineral acids. Furthermore the defoaming agent should act over a long period, i. e. the good deaerating agents
defoaming agent with the best initial effect (spontaneous effectiveness) is not necessarily the
best defoaming agent. In the same way not all defoaming agents are at the same time good
deaerating agents.
Numerous surface active substances, e. g. some non-ionic alkylene oxide adducts, are known Surface active substances,
to act as defoamers. Just as important as these are the defoaming and deaerating agents which e. g. alkylene oxide adducts
are produced from formulations of different substances. Components of such formulations may
include the following: Formulations

Alkylene oxide adducts

Hydrocarbons (including mineral oils, white oil, paraffins)
Alcohols
Fatty acids
Fatty acid salts of multivalent cations
Esters (including fats, waxes, phosphoric esters)
Amides (including amide waxes)
Silicone oils
Silicas

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Defoaming and deaerating agents can be appropriately classified according to their chemical Chemical composition
composition, as follows: of defoaming and
deaerating agents
Fat defoamers
Fat defoamers are products containing a fat substance as their effective component.
They may, however, also contain hydrocarbons, alcohols and emulsifiers.
Alkylene oxide adducts or defoaming agents containing alkylene oxide adducts
Defoaming agents of this type contain non-ionic alkylene oxide adducts as effective
substance. They may, however, also contain hydrocarbons, alcohols, esters, water and
emulsifiers.
Defoaming agents containing metal soaps
Defoaming agents containing metal soaps include fatty acid salts of multivalent cations
(e. g. calcium, aluminium) as effective substance. Hydrocarbons, alcohols and esters
are used as solvents or dispersing agents, and an emulsifier may also be additionally
included.
Silicone or silicone containing defoaming agents
Silicone or silicone containing defoaming agents include silicone oils as effective com-
ponent. Hydrocarbons, alcohols, esters, alkylene oxide adducts and emulsifiers may
also be included.
Wax defoaming agents
Wax defoaming agents contain a finely dispersed wax (dispersed phase) as effective
substance. Hydrocarbons, alcohols and esters are used as dispersing agents, and
emulsifiers may also be additionally included.
Dispersion defoaming agents
Dispersion defoaming agents are dispersions (suspensions, emulsions) of hydrocar-
bons, alcohols and esters in water containing dispersing agents and generally also contain
an emulsifier.
Sulpho-carboxylic ester defoaming agents
These defoaming agents contain a sulpho-carboxylic ester as the effective component.
The alcohol, which has a defoaming effect, is gradually formed by hydrolysis under
extreme pH conditions.

Defoaming agents can also be differentiated according to their behaviour during application.
There are soluble (see explanation on turbidity point of alkylene oxide adducts), emulsifiable
(finely to coarsely dispersed) and non-emulsifiable defoaming agents.
Many defoaming agents are very specific in their effectiveness, i. e. the most suitable defoaming Selection of the correct
agent must generally be selected empirically. Therefore, in order to select the correct defoam- defoaming agent by
ing agent a practical foam test must generally be carried out in the laboratory. carrying out practical
foam tests in the
laboratory

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3.6 Recommended Fields of Application for ANTISPUMIN® Defoaming and Deaerating Agents

Antispumin KA 01

Antispumin WA 2
Antispumin S 664

Antispumin 7100
Antispumin 7500
Antispumin ASW

Antispumin SGM
Antispumin LVW
Antispumin NPK
Antispumin HW

Antispumin WA

Antispumin ZLP
Antispumin GH
Antispumin BA
Antispumin AZ

Antispumin HE

Antispumin ZU
Antispumin DS

Antispumin ZK
Antispumin TZ
Antispumin SP
Antispumin TS
Antispumin AI
Mining
Salt pastes for dust binding
Chemical industry
Effluent
Bauxite extraction (white operation)
Dispersion paints
Emulsion polymerisation
Gas washing
Gelatine (solutions, emulsions)
Sewage plant (biological, mechanical)
Paint spraying cabins
Sea water desalination
Metal working oil emulsions
Methyl cellulose production
Mineral fibre industry, process water
Phosphoric acid production (wet)
Super phosphate extraction
Surfactant solutions (alkaline)
Compound fertilizer production
Washing and dry cleaning solutions
Paper and cellulose industry
Cellulose production
Pulp
Size press
Coating
Effluent
Food industry, biotechnological processes
Alkohol distillation
Alkohol fermentation
Amino acid production
Fermentation processes
Bottle cleaning plants
Yeast production
Potato processing
Effluent/wash water
Effluent
Starch production
Protein extraction
Cheese factory effluent
Dairy effluent
Pectin production (effluent)
Slaughterhouse
Effluent
Scalding plant
Starch saccharification
Sugar extraction from beet
Outside operation
Inside operation

In addition to the ANTISPUMIN products listed here, test products are permanently being developed for special fields of appli-
cation. Please contact our sales engineers or our technical application division for information concerning these products. With
respect to their use in the food industry, please also note the information contained in chapter 5.
20
4. Testing of Defoaming and Deaerating Agents in the Laboratory

There are a number of different methods of testing the effectiveness of ANTISPUMIN® products
in the laboratory. Foam is produced with the medium to be defoamed or deaerated by shaking,
stamping, stirring, (pump) circulating or introducing air (or gas). The ANTISPUMIN products
can be added either before or during the application of mechanical force (after foam has al-
ready been produced), or in individual cases also afterwards. It is important that all parameters Constant parameters
are kept constant during the test.

Optimal ANTISPUMIN products for solving foam problems can be selected with laboratory
tests. The precise dosing quantities required have to be determined by field tests at the plant.

4.1 General Selection Criteria for Defoaming and Deaerating Agents

In order to limit the selection from the range of possible ANTISPUMIN products right from the
start, the following criteria should be first clarified:

Type of medium (e. g. protein or surfactant-containing effluent) Criteria

Temperature of medium
(it is essential that this is also observed during the laboratory tests)
pH-value
How is the foam produced (e. g. by stirring or pumping)?
Is a long-term effect of the defoaming product necessary
(e. g. in a closed loop process)?
Should the ANTISPUMIN product be used in diluted form, i. e. must it
be emulsifiable?
Are authorisation documents required for the defoaming product
(e. g. FDA, BfR, HACCP)?
Other requirements (e. g. degradability, toxicology, sterilizability)

The more exact the general criteria for defoaming and deaerating agents are investigated at
the place of application, the greater is the probability that the ANTISPUMIN product which is
suitable in the laboratory tests will also guarantee an optimum problem solution in later opera-
tion.

4.2 Laboratory Tests with ANTISPUMIN® Defoaming and Deaerating Agents

When carrying out laboratory tests with ANTISPUMIN products, it should be ensured that the
test apparatus is thoroughly cleaned each time after use. Unsatisfactory cleaning, i. e. residues
of defoaming agent left in the apparatus, may be the cause of significant deviations, and therefore
faulty assessment of the test results.

21
4.2.1 Shaking Method

The shaking method is very easy to carry out, and is suitable as a rapid orientation test to deter-
mine the most suitable ANTISPUMIN® product for the particular foam problem. This test can
also be carried out locally. Screw cap glass jars are half filled with the medium to be defoamed;
1 drop of each different product is put onto the surface of the medium in each of the jars by
means of a thin glass rod. The jars are then closed and each is shaken in the same way for the
same time.

This method can only be carried out with media which foam relatively easily (otherwise either
no foam is produced or 1 drop of each ANTISPUMIN product is too high a dosage). It only
shows the spontaneous effect, but not the long-term effect of an ANTISPUMIN product.

Comparison with a blank (without addition of a defoaming product), or comparison of the jars
with each other, immediately and after a certain standing time, generally shows clearly which
ANTISPUMIN products are suitable (see figure 12).

Test parameters are:

Duration or frequency of shaking,
Test temperature and
Quantity of the particular ANTISPUMIN product added.

Defoaming agents:
0 1 2 3 4 5
0 Without
Drawing oil
emulsion from 1 ANTISPUMIN
a wire-drawing Fat defoaming agent type
plant
2 ANTISPUMIN
Alkylene oxide adduct type
Effluent 3 ANTISPUMIN
containing Metallic soap containing
surfactant and
protein defoaming agent type
4 ANTISPUMIN
Wax defoaming agent type
Surfactant solution
(INTRASOL® NP 9) 5 ANTISPUMIN
Dispersion defoaming
agent type
Fig. 12: Selection of the correct ANTISPUMIN product using the shaking method (500 ml jars)

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4.2.2 Perforated Disc Impact Method

This test is carried out based on DIN 53 902. The criteria used for assessing the effectiveness Foam volume and
of an ANTISPUMIN® defoaming agent are the foam volume and foam stability. The foam is foam stability
produced by stamping onto the test medium in an upright cylinder with a perforated disc fitted
onto a handle. In order to determine the foam volume and stability, the quantity of foam produced
is measured immediately after stamping and after standing for a certain time.

Test parameters are:

Test temperature and
Quantity of the particular ANTISPUMIN product added.

The perforated disc impact method is suitable for quick testing, e. g. for synthetic plastic dis- Quick testing
persions which may be stored for several months after addition of an ANTISPUMIN defoam-
ing agent. In this case samples can be taken at certain intervals, and the “actual condition” with
respect to foaming behaviour can be determined. This method gives no information about the Foam behaviour
long-term effect of an ANTISPUMIN defoaming agent.

200

Foam stamper (perforate

disc fitted to a handle)
Foam number in [ml]

100
1.1 Immediately
1.2 After 12 weeks

0
0 1 5 10
Time in [min]
Perforated disc Test medium: Synthetic plastic dispersion
(ethene/vinyl acetate copolymer)
1000 ml measuring Volume: 200 ml
cylinder Temperature: 20 - 25 °C
Defoaming agents: 0 = Without
1 = ANTISPUMIN Wax
defoaming type (0.30 %)

Fig. 13: Perforated disc impact method Fig. 14: Foam stability using an ANTISPUMIN
defoaming agent

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4.2.3 Stirring Method

A certain quantity of the test medium to which a small quantity (generally 5 – 100 ppm) of
the selected ANTISPUMIN® defoaming agent has been added, is intensively stirred (gener-
ally using a propeller stirrer, n = 1000 – 2000 min-1) at the test temperature (temperature at the
sampling point for the test medium). The height to which the foam rises or the extent to which Rise and collapse of foam
it collapses after switching off the stirrer, is measured in relation to time.

Test parameters are:

Test volume,
Stirrer type,
Stirrer speed,
Stirring time and
Quantity of particular ANTISPUMIN defoaming agent added.

The effectiveness of the ANTISPUMIN defoaming agent depends on the shear intensity (rota-
tions of stirrer) and the length of time the shear force is applied.

The results obtained by the stirring method can be correlated to shear sensitivity and the long- Shear sensitivity and long-
term effect of an ANTISPUMIN product in a given test medium. term effect

Stirrer 80
70
60
Foam height in [mm]

50
Glass beaker
40
30
20
10
0
0 5 10 15 20 25 30
Time in [min]

Test medium: Potato fruit water

Volume: 1000 ml
Temperature: 70 ± 5 °C
Stirrer speed: 1500 min-1
Measurement of Defoaming agents: 0 = Without
foaming height with a ruler 1 = ANTISPUMIN Fat defoaming agent type
2 = ANTISPUMIN Alkylene oxide adduct type
(100 ppm of each type)

Fig. 15: Stirring method (without heating) Fig. 16: Effectiveness of various ANTISPUMIN
products tested using the stirring
method

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4.2.4 Pump Circulation Method

In the pump circulation method foaming is produced by circulating the test medium at the test
temperature (temperature at the sampling point of the test medium). Various types of pumps
can be used, e. g. centrifugal, tubular and diaphragm. The height of the foam or the extent to
which the foam collapses after switching off the pump is measured in relation to time. Rise and collapse of foam

Test parameters are:

Test volume,
Height of fall (from tube outlet to surface of test medium),
Pump type,
Pump performance,
Pumping time and
Quantity of particular ANTISPUMIN® defoaming agent added.

The shear force applied in this method is different to that in the stirring method. The pump
circulation method gives results which can be correlated to shear sensitivity (during pumping), Shear sensitivity and long-
and the long-term effect of an ANTISPUMIN defoaming agent in a certain test medium. term effect
Total volume in measuring cylinder in [ml]

1100
1000
Pump Glass tube 0
900
800
Bunsen
valve 700 1
600
Silicone tube 500
400
Total volume without foam
300
Measuring 0
cylinder
0 10 20 30 40 50 60 70 80 90 100 110 120
Time in [min]

Test medium: Lye from sulphate pulp

production (pH approx. 13)
Volume: 500 ml
Temperature: 60 - 90 °C
Bath Pump delivery: 90 l/h
Height of fall: 350 mm
Defoaming agent: 0 = Without
1 = ANTISPUMIN Wax
defoaming agent type
(200 ppm)

Fig. 17: Pump circulation method Fig. 18: Long-term effect of an ANTISPUMIN
product tested using the pump
circulation method

25
4.2.5 Air (or Gas) Injection Method

In this test air or gas is blown through a sinter plate at the lower end of a vertically standing tube,
which is partly filled with the test medium, and the height or drop of the foam level is measured
in relation to time. The particular ANTISPUMIN® defoaming agent can be put on the foam im-
mediately before the beginning of the test or during the test. If the product is put on an already
existing foam, its spontaneous attack can be very well observed.

Test parameters are:

Test volume,
Test temperature (only limited),
Volume of air (or gas) introduced per time unit,
Duration of air (or gas) injection and
Quantity of particular ANTISPUMIN defoaming agent added.

400
Transparent
Foam height in [mm]

plastic tube
300

200
Sinter plate
100

0
Rotometer
0 5 10 15 20 25 30
Time in [min]

Gas

Test medium: Effluent from methyl

cellulose production
Volume: 500 ml
Temperature: 20 ± 2 °C
Air: 300 l/h
Defoaming agent: 0 = Without
Outlet
1 = ANTISPUMIN Alkylene
oxide adduct type
(100 ppm)

Fig. 19: Air (or gas) injection method Fig. 20: Long-term effect of an ANTISPUMIN
defoaming agent tested using the air
injection method

4.2.6 Special Test Methods

Special test methods have been developed for testing the effectiveness of defoaming products
in a few processes in the chemical industry, e. g. wet attack of phosphate rock with mineral
acids. In this process the attacked rock mixture foams mainly because of gases formed during
the attack process.

26
5. Defoaming Agents for Food and Animal Feed

For the production of a commodity that comes into contact with food or a processing auxiliary Requirements
used in the production of a foodstuff, special requirements are placed on process auxiliaries.

Examples of Listings, Laws and State Recommendations:

USA FDA paragraphs

Europe The CoE´s Paper Resolution
Germany BfR recommendations

USA Opinion Letter

Europe HACCP analysis and/or migration analyses

Before use as a process or processing auxiliary in the production of foodstuffs, a checklist has
to be completed. Analysis is carried out on the basis of the details provided concerning whether
the statutory preconditions for use in the food industry have been fulfilled.

6. Solution for your Foam Problems

Our laboratory experts will be pleased to help you in selecting the suitable test method. For tests
in our laboratory a representative sample (approx. 10 – 20 l) of the medium to be defoamed
should be submitted. Taking into account the general selection criteria stated under section 4.1,
our technical staff will propose the suitable ANTISPUMIN® defoamer for a plant trial.

27
® Registered trademark, Ashland | © 2008, Ashland | March 2008, V02

All statements, information and data presented herein are believed to be accurate and reliable but are not to be taken as a gua- Ashland Deutschland GmbH
rantee, express warranty or implied warranty of merchantability or fitness for a particular purpose, or representation, express Ashland Water Technologies
or implied, for which seller assumes legal responsibility, and they are offered solely for your consideration, investigation and Fütingsweg 20, D-47805 Krefeld
verification. Statements or suggestions concerning possible use of this product are made without representation or warranty P.O. Box 10 04 52, D-47704 Krefeld
that any such use is free of patent infringement and are not recommendations to infringe on any patent. Phone: +49 2151 38 3052
Fax: +49 2151 38 1106
water@[Link]
[Link]

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