Chapter 21

D e f o a m e r s

Defoaming is necessary in several industrial branches and is often a key factor

for efficient operation. A review on defoamers is given by Owen [1381] in
Kirk-Othmer.

Uses in Petroleum Technology

Gas-Oil Separation
Defoamers are used in oil extraction, such as in drilling muds and cemen-
tation, and also directly with crude oil itself. In its natural state, a crude oil
contains dissolved gases at the pressure of the reservoir. When the pressure is
reduced, the gases are liberated and troublesome foam can develop. There are
three ways to prevent foaming in gas-oil separation:
1. Based on prior knowledge of crude oil foaming properties, a separator
large enough to cope with foam formation may be installed.
2. The amount of foam can be reduced by injecting a defoamer.
3. The gas-oil separator can be equipped with a mechanical device to de-
stroy or prevent a presumptive foam.
Understanding the factors that inhibit the foaming power is of great impor-
tance, because it yields a basic knowledge—how the materials produced will
perform with respect to foaming. It also serves to predict how individual crude
oil compositions would work with different defoamers [301].

Cleaning of Sour Gas

Desulfurization of natural gas can be achieved by bubbling it through an
alkaline solution. Defoamers are added to avoid foaming.
Distillation and Petroleum Production
Air entrainment and foaming in hydrocarbon liquids can cause operational
problems with high-speed machinery in physical-chemical processes such as
petroleum production, distillation, cracking, coking, and asphalt processing.

Classification of Defoamers
Defoamer formulations currently contain numerous ingredients to meet the
diverse requirements for which they are formulated. Various classification
approaches are possible, including classification by application, physical form
of the defoamer, and the chemical type of the defoamer. In general, defoamers
contain a variety of active ingredients, both in solid and in liquid states, and a
number of ancillary agents such as emulsifiers, spreading agents, thickeners,
preservatives, carrier oils, compatibilizers, solvents, and water.

Active Ingredients
Active ingredients are the components of the formulation that control the
actual foaming. These may be liquids or solids.

Liquid Components
Because lowering the surface tension is the most important physical property
of a defoamer, it is reasonable to classify the defoamer by the hydrophobic
operation of the molecule. In contrast, the classification of organic molecules
by functional groups are often polar and hydrophilic (i.e., alcohol, acid, and
salt are common in basic organic chemistry). Four classes of defoamers are
known as liquid phase components:
• Hydrocarbons
• Polyethers
• Silicones
• Fluorocarbons

Synergistic Antifoam Action by Solid Particles

Often, dispersed solids are active in defoaming in suitable formulations.
Some liquid defoamers are believed to be active only in the presence of a
solid. It is believed that a surface-active agent present in the system will carry
the solid particles in the region of the interface and the solid will cause a
destabilization of the foam.
 For example, a synergistic defoaming occurs when hydrophobic solid par-
ticles are used in conjunction with a liquid that is insoluble in the foamy solu-
tion [652]. Mechanisms for film rupture by either the solid or the liquid alone
have been elucidated, along with explanations for the poor effectiveness, which
are observed with many foam systems for these single-component defoamers.

Silicone Antifoaming Agents

Polydimethylsiloxane is active in nonaqueaous systems, but it shows little

foam-inhibiting effect in aqueous systems. However, when it is compounded
with a hydrophobic-modified silica, a highly active defoamer emerges.
Several factors contribute to the dual nature of silicone defoamers. For ex-
ample, soluble silicones can concentrate at the air-oil interface to stabilize
bubbles, while dispersed drops of silicone can accelerate the coalescence pro-
cess by rapidly spreading at the gas-liquid interface of a bubble, causing film
thinning by surface transport [1163].
Silicones exhibit an apparently low solubility in different oils. In fact, there
is actually a slow rate of dissolution that depends on the viscosity of the oil
and the concentration of the dispersed drops. The mechanisms of the critical
bubble size and the reason a significantly faster coalescence occurs at a lower
concentration of silicone can be explained in terms of the higher interfacial
mobility, as can be measured by the bubble rise velocities.

Ancillary Agents
In addition to the defoamer itself, certain ancillary chemicals are incorpo-
rated into the formulation, for example, to effect emulsification or to enhance
the dispersion.

Surface-Active Components

Emulsifiers are essential in oil-water emulsion systems. For example, oil-

in-water emulsifiers are used to promote the dispersion in aqueous foaming
systems.

Carriers

The formulation of a defoamer should be suitable for a prolonged storage

time before use. A carrier system makes the defoamer easy to handle and dis-
persible for delivering the active defoamer components to the foaming system
and also to stabilize the defoaming formulation.
Often, carriers are low-viscosity organic solvents. Aliphatic hydrocarbons
are most commonly used as carriers. The carrier itself may also exhibit
defoaming properties. Water is often used as carrier fluid. Here the defoamer
formulation is typically an oil-in-water emulsion.

Theory of Defoaming
Stability of Foams
Foams are thermodynamically unstable but are prevented from collapsing
by the following properties:
• Surface elasticity
• Viscous drainage
• Reduced gas diffusion between bubbles
• Thin-film stabilization effects from the interaction of opposite surfaces
The stability of a foam can be explained by the Gibbs elasticity (E). The
Gibbs elasticity results from reducing the surface concentration of the active
molecules in equilibrium when the film is extended. This causes an increase
in the equilibrium surface tension a, which acts as a restoring force.

E = 2A^- (21-1)
dA
A is the area of the surface. In a foam, where the surfaces are intercon-
nected, the time-dependent Marangoni effect is important. A restoring force
corresponding to the Gibbs elasticity will appear, because only a finite rate
of absorption of the surface-active agent, which decreases the surface tension,
can take place on the expansion and contraction of a foam. Thus the Marangoni
effect is a kinetic effect.
The surface tension effects under nonequilibrium conditions are described
in terms of dilatational moduli. The complex dilatational modulus 8 of a single
surface is defined in the same way as the Gibbs elasticity. The factor 2 is not
used in a single surface.

(21-2)

In a periodic dilatational experiment, the complex elasticity module is a

function of the angular frequency:

(21-3)

Ed is the dilatational elasticity, and rja is the dilatational viscosity. It is

characteristic for a stable foam to exhibit a high surface dilatational elasticity
and a high dilatational viscosity. Therefore effective defoamers should reduce
these properties of the foam.
 Table 21-1
Dilatational Elasticities and Viscosities of Crude Oil at 1 mHz with
Polydimethylsiloxanes (PDMS) [300]

Amount of PDMS
Crude oil (ppm) £j (mNm"1) rjd (mNsm" 1 )
North Sea none added 1.34 153
North Sea 12,500 0.69 90
North Sea 60,000 0.51 33
Middle East none added 1.63 105
Middle East 60,000 1.19 53

This has been verified for polydimethylsiloxanes added to crude oils. The
effect of the dilatational elasticities and viscosities on crude oil by the addition
of polydimethylsiloxanes is shown in Table 21-1. Under nonequilibrium con-
ditions, both a high bulk viscosity and a surface viscosity can delay the film
thinning and the stretching deformation, which precedes the destruction of a
foam. There is another issue that concerns the formation of ordered structures.
The development of ordered structures in the surface film may also stabilize the
foams. Liquid crystalline phases in surfaces enhance the stability of the foam.
If the gas diffusion between bubbles is reduced, the collapse of the bubbles
is delayed by retarding the bubble size changes and the resulting mechani-
cal stresses. Therefore single films can persist longer than the corresponding
foams. However, this effect is of minor importance in practical situations. Elec-
tric effects, such as double layers, form opposite surfaces of importance only
for extremely thin films (less than 10 nm). In particular, they occur with ionic
surfactants.

Action of Defoamers
At high bulk viscosity, lowering the surface tension is not relevant for the
mechanism of stabilization of foams, but for all other mechanisms of foam
stabilization a change of the surface properties is essential. A defoaming agent
will change the surface properties of a foam upon activation. Most defoamers
have a surface tension in the range of 20 to 30 mNm" 1 . The surface tensions
of some defoamers are shown in Table 21-2.
Two related antifoam mechanisms have been proposed for low surface ten-
sions of certain defoamer formulations:
1. The defoamer is dispersed in fine droplets in the liquid. From the droplets,
the molecules may enter the surface of the foam. The tensions created
by this spreading result in the eventual rupture of the film.
 Table 21-2
Surface Tensions of Some Defoamers

Surface tension at 200C

Material (mNm"1)
Polyoxypropylene 3000 Dalton 31.2
Polydimethylsiloxane 3900 Dalton 20.2
Mineral oil 28.8
Corn oil 33.4
Peanut oil 35.5
Tributyl phosphate 25.1

2. Alternatively, it is suggested that the molecules will form a monolayer

rather than spreading. The monolayer has less coherence than the original
monolayer on the film and causes a destabilization of the film.

Spreading Coefficient. The spreading coefficient is defined as the difference

of the surface tension of the foaming medium a / , the surface tension of the
defoamer a j , and the interfacial tension of both materials o j / .

S = Gf-Gd- adf (21-4)

It can be readily seen that the spreading coefficient S becomes increasingly

positive as the surface tension of the defoamer becomes smaller. This indicates
the thermodynamic tendency of defoaming.
The above statements are adequate for liquid defoamers that are insoluble in
the bulk. Experience has proven, however, that certain dispersed hydrophobic
solids can greatly enhance the effectiveness of defoaming. A strong correlation
between the effectiveness of a defoamer and the contact angle for silicone-
treated silica in hydrocarbons has been established [300]. It is believed that the
dewetting process of the hydrophobic silica causes the collapse of a foam by
the direct mechanical shock occurring by this process.

Examples for Application

Aqueous Fluid Systems

Alcohols. Higher aliphatic alcohols with polyethyleneoxide and poly-

propyleneoxide are particularly effective at reducing the gas content of drilling
solutions [1442].
An aliphatic alcohol with 8 to 32 carbon atoms can be used together with a
solid carrier. The carrier is nonswelling in aqueous media and consists of small
particles with an average size of less than 150 to 200 |n. The carrier adsorbs the
alcohol [1439,1440]. Some examples for solid carrier materials are sawdust,
ground rice hulls, ground nut shells, and clays. Other carrier materials may
include solids that are commonly added to drilling and other well fluids as
fluid loss additives, bridging agents, and the like.

Fatty Acid Esters. Defoamers that are more environmentally acceptable than
convential products are based on fatty acid esters of hydroxy alcohols, such
as sorbitan monooleate [1908] or sorbitan monolaurate in combination with
diethylene glycol monobutyl ether as a cosolvent [451]. These defoamer com-
positions are as effective as conventional materials, for example, those based
on acetylenic alcohols are less toxic, especially to marine organisms, and are
readily biodegradable. The defoamer compositions are used in water-based
hydrocarbon well fluids during oil/gas well drilling, completion, and workover,
especially in marine conditions.

Aerosil. Aerosil as a solid additive in combination with diesel is active as a

defoamer [962]. The aerosil is modified with bifunctional silicoorganic com-
pounds. The composition is added to drilling solution in the form of a 3% to
5% suspension, in an amount of 0.02% to 0.5% by weight of aerosil per weight
of drilling solution.

Polyoxirane. Polyoxirane-containing formulations have a low cloud point,

good ability to reduce surface and interfacial tensions, good wettability, and
limited tendency to dispersion. The oxirane-methyloxirane copolymers [1176]
are nontoxic and show high stability in both acidic and alkaline environ-
ments. Their poor stability against oxidation can be improved through chemical
modification (blocking hydroxide groups) or by using an alkaline catalyst,
which acts as an inhibitor of the self-oxidation process.
Polypropylene glycol, particulate hydrophobic silica, and a fatty acid methyl
ester, or an olefin or linear paraffin as a liquid diluent, are proposed for well-
stimulation jobs [357].

Plugging Agents

The foaming of plugging agents with a large content of lignosulfonate can be

prevented by introducing a drilling mud antifoaming agent, consisting of poly-
methylsiloxane and tributyl phosphate [1905]. A synergistic effect is observed,
in that polymethylsiloxane simultaneously displaces the adsorbed molecules of
the foam stabilizer (lignosulfonate) from the foam film, and tributyl phosphate
reduces the surface viscosity of the film.
Degassing Crude Oil
Fluorosilicones and Fluorocarbons. Early defoamers to remove gas from
crude oil consisted of chlorofluorocarbons. The use of these compounds has
essentially ceased. They were substituted gradually by pure fluorosilicones
[302]. A formulation that is free of chlorofluorocarbons was described in the
early 1990s.
A water-continuous emulsion, suitable for use as an antifoam additive, con-
tains 85% to 98% by weight of afluorosiliconeoil and 2% to 15% by weight
of an aqueous surfactant solution [1722]. The additive is suitable for use in
separation of crude oil that contains associated gas. The additive may be used
in both aqueous and nonaqueous systems and allowsfluorosiliconeoils to be
used without the need for environmentally damaging chlorofluorocarbons.
Freshly extracted degassing crude oil can be defoamed withfluorinatednor-
bornylsiloxanes [171]. The compounds are highly effective and show a broad
area of application for defoaming degassing crude oils of different origins. The
compounds can be used in concentrations as small as 20 ppm.

Polydienes. Polydienes that are modified with organosilicons have been de-
scribed and find application as antifoaming and/or deaeration agents for oil
field treating of crude oil [170].

High- Temperature Defoamers. Polyisobutylene compounds are particularly

effective in high-temperature (300° to 1000° F) treatments of hydrocarbon
fluids [786,788], such as during the distillation of crude oil and coking of crude
oil residues. Polyisobutylene compounds are less expensive than silicone-based
compounds.

Natural Gas
A mixture of dialkylphthalate of higher isoalcohols, in excess of the respec-
tive isoalcohols, is used as an antifoaming composition in purification of natural
gas where H2S and CO2 are removed by aqueous solution of amine [474].
Amyl alcohol and diethyldisulfide are used to improve the properties of
a defoaming formulation for the removal of acidic components from natural
gas [H]. The mixture contains 35% to 50% by weight tributyl phosphate and
20% to 25% by weight amyl alcohol. The rest, diethyldisulfide, is an industrial
waste.
Esters, for example, dialkyl polypropyleneglycol adipate and dibutyl adi-
pate, also find use as defoamers in the removal of H2S and CO2 from natural
gas by bubbling it through an amine solution [659]. Use of the aforementioned
components increases the efficiency of foam destruction.
 tert-Amyl alcohol Diethyldisulfide

Dibutyl adipate

Figure 21-1. Amyl alcohol, diethyldisulfide, and dibutyl adipate.

Antimicrobial Antifoam Compositions

In addition to the typical constituents of a defoamer formulation (i.e., a

primary antifoam agent with high surface area, such as silica, and a secondary
antifoam agent for acting synergistically with the primary antifoam agent,
such as polydimethylsiloxane), a water carrier with a quaternary ammonium
salt silane compound [689] can be included, which acts as an antimicrobial
agent. The silane is fixed to the surface of the silica. The composition makes
the defoamer composition resistant to biologic degradation because of the
presence of microorganisms in the system.