Superheated Water

Extraction (SWE)
A. Ahmadpour
Chemical Eng. Dept.
Ferdowsi University of Mashhad
 Contents
Introduction
Change of properties with temperature
Explanation of anomalous behavior
Effect of pressure
Solubility in superheated water
Separations Using Superheated Water
 Applications of superheated water extraction
 Comparisons with other extraction methods
 Equipment
Conclusion
2
 References
1. Green Separation Processes. Edited by C. A. M.
Afonso and J. G. Crespo, 2005

2. US patent website, http://patft.uspto.gov

3. R.M. smith/ J. Chromatogr. A 975 (2002) 31-46

4. http://www.wikipedia.org/superheated-water.mht

3
 Introduction

We will concentrate on work using

superheated water as a replacement for
organic solvents for extractions,
chromatography and related processes

4
 Cont.
? What is superheated water?

 Superheated water is liquid water under

pressure at temperatures between the usual
boiling point (100°C) and the critical
temperature (374°C).

5
 Cont.
 The pressures required to maintain a condensed state of water
are moderate, 15 bar at 200°C and 85 bar at 300°C

Note:
If the pressure drops below the boiling point at any pressure,
superheated steam is formed.

That behaves quite differently as an extraction solvent to

superheated water.

6
 Change of properties with
temperature

 The properties of all materials change with

temperature,
but water shows changes which are much
greater than would be expected from
temperature considerations alone.

7
 Cont.

Viscosity
Surface tension of drops
Diffusivity
When T Specific heat capacity @ p=cte

Dielectric constant

8
 Cont.

 Specific heat capacity at constant pressure

increases with temperature, from 4.187 kJ/kg
at 25°C to 8.138 kJ/kg at 350°C.

9
 Cont.

 The dielectric constant (relative permittivity)

decreases significantly as the temperature
rises, which has a significant effect on the
behavior of water at high temperatures.

10
 Explanation of anomalous behavior

 Many of the anomalous properties of water are

due to very strong hydrogen bonding.

11
 Cont.
 Over the superheated temperature range, the extensive
hydrogen bonds break down.

 Water effectively becomes less polar and behaves more like

an organic solvent such as methanol or ethanol.

 Solubility of organic materials and gases increases by

several orders of magnitude.

12
 Cont.
 Water is a polar molecule

 In an applied electric field, the molecules align with the

field

 In water, the extensive hydrogen bonded network tends

to oppose this alignment, and the degree to which this
occurs is measured by the relative permittivity
(dielectric constant)

13
 Cont.
 Because of its extensive hydrogen bonds, water has a
high relative permittivity, about 80 at room
temperature (Ɛ=80). This allows water to dissolve salts.

 As the temperature increases, the thermal motion of

the molecules disrupts the hydrogen bonding
network, and therefore the relative permittivity
decreases with temperature, to about 7 at the critical
temperature.

14
 Cont.

 At 205°C the relative permittivity has fallen to 33

(Ɛ=33), the same as methanol at room temperature.
 Thus, from 100°C to 200°C water behaves like a
water / methanol mixture.

15
 Cont.

Green Separation Processes. Edited by C.A.M. Afonso and J.G. Crespo

16
 Effect of pressure

 At temperatures below 300°C water is fairly

incompressible, which means that:

 Pressure has little effect on the physical properties of

water, provided it is sufficient to maintain liquid state.
 This pressure is given by the saturated vapor pressure, and
can be looked up in steam tables.

17
 Cont.
 For example:
the saturated vapor pressure at :
 121°C is 100 kPa
 150°C is 470 kPa
 200°C is 1550 kPa

 The critical point is 21.7 MPa at a temperature

of 374°C.

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 Solubility in superheated water
 Organic compounds

 Salts

 Gases

19
Solubility of organic compounds
 Organic molecules often show a dramatic increase
in solubility in water as the temperature rises.
There are 2 reasons for this behavior:

I. the polarity change

II. the solubility of sparingly soluble materials tends to

increase with temperature as they have a high positive
enthalpy of solution

20
 Cont.
 Some organic compounds which can dissolve
in superheated water are:
 Polycyclic aromatic hydrocarbon (PAHs)

 Naphthalene

 Polychlorinated biphenyl (PCBs)

21
 Cont.

 The solubility of PAH’s

increased by 5 orders of
magnitude from 25°C to
225°C and naphthalene,
for example, forms a 10
wt% solution in water at
270°C.
Green Separation Processes. Edited
by C.A.M. Afonso and J.G. Crespo
22
 Solubility of salts
 Despite the reduction in relative permittivity, many salts
remain very soluble in superheated water until the critical
point is approached.

 For example:
Sodium chloride, dissolves 37 wt% at 300°C

Note:
As the critical point is approached, the solubility drops markedly
to a few ppm, and salts are hardly soluble in supercritical water.

23
 Solubility of Gases
 The solubility of gases in water is usually thought to decrease
with temperature, but this only occurs to a certain temperature,
then solubility increases again.

 For example:
For nitrogen, this minimum is 74°C and for oxygen it is 94°C

Therefore, gases are quite soluble in

superheated water at elevated pressures.

24
 Separations Using Superheated
Water
 History
 Superheated water extraction
 Applications of superheated water
extraction
 Comparisons with other extraction methods
 Equipment

25
 History
 Liquid water at elevated temperatures above its boiling point
has been used for many years as an industrial solvent and
cleaning agent in applications ranging from:

 enhancing the extraction of oil shale

 the extraction of sulphur from ore bodies to degreasing

 As a vapor, steam is commonly used in :

 hydro distillation for the isolation of volatile constituents of plant

materials to provide essential oils of value in perfumery.

26
 Cont.

 The recent analytical interest in superheated

water as an extraction solvent began with the
work of Hawthorne who was interested in
environmentally friendly extraction methods
for soils and environmental solids.

27
 Superheated water extraction
a) Extraction using superheated water tends to be fast because
diffusion rates increase with temperature.

b) Organic materials tend to increase in solubility with

temperature.

 Therefore,
extraction with superheated water can be both selective and
rapid.

28
 Applications of superheated water
extraction
 Examples of separations include:
1) the removal of pesticides from contaminated soil
including removal in situ,
2) the removal of organic pollutants from
wastewater,
3) the extraction of organic compounds from solids,
4) the extraction of compounds from solids coupled
with degradation,

29
 Cont.
5) the extraction and degradation of chemical warfare
agents,
6) the extraction of synthesis contaminants and organic
compounds from polymers or plastics,
7) the extraction of biologically active organic
compounds from plant tissue,
8) the extraction and reaction of compounds from plant
tissue to produce flavors and fragrances,
9) as a mobile phase for liquid chromatography.
30
R.M. smith, J. Chromatogr. A 975 (2002) 31-46 31
R.M. smith, J. Chromatogr. A 975 (2002) 31-46
32
R.M. smith, J. Chromatogr. A 975 (2002) 31-46
33
R.M. smith, J. Chromatogr. A 975 (2002) 31-46

34
 Comparisons with other extraction
methods
 Many of the reports have compared SWE
with previously reported methods, such as:
Soxhlet extraction, SFE and steam distillation
for plant materials.
 For most environmental samples the results
were generally similar to previous methods
although there were some interesting
variations.
35
 Cont.
All of these methods had attributes but water
was judged the best overall because of:
 Its low price
 Good availability
 Environmental safety
 Lower energy requirements

36
 Cont.
 The energy required to heat water is significantly
lower than that needed to vaporize it (for example for
steam distillation), and the energy is easier to recycle
using heat exchangers.

 To heat water at 25°C to steam at 250°C and 1 atm

requires 2869 kJ/kg.
 To heat water at 25°C to liquid water at 250°C and
50 atm requires only 976 kJ/kg.

37
 Cont.

 Therefore:
the energy use for superheated water
extraction is less than one sixth needed for
steam distillation.

38
 Equipment
 Most SWE have employed relatively simple
home made equipment because pressure is not
a critical factor in SWE due to the low
compressibility of water over the typical
temperature ranges.
 Therefore, the pressure control can be very
basic and accurate measurement and control is
not required.

39
 Cont.
Laboratory-scale Extraction

Green Separation Processes. Edited by C.A.M. Afonso and J.G.

Crespo
40
 Cont.
Pilot-plant Equipment

Green Separation Processes. Edited by C.A.M. Afonso and J.G. 41

Crespo
 Conclusion
 Superheated water extractions have been shown to be
feasible with particular interest in avoiding the need
for organic solvents in environmental extractions or
in pharmaceutical or food samples.
 The method is thus environmentally friendly, cheap
and nontoxic.
 The equipment required is relatively simple and
avoids the need for the high pressures employed in
SFE.

42
 Cont.

 unlike carbon dioxide, there is no problems

with cooling and condensation.
 Most samples have been solid matrices, such
as soils and plant materials.

43