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Draft September 7, 2013 September 11, 2013 September 13, 2013 September 14, 2013
A New Direction for Chemical Engineering:
Continuous Reactions in Neowater
G. GRAHAM ALLAN
GREGORY M. KEGEL
THOMAS E. LOOP
UNIV. of WASHINGTON, SEATTLE
ONE SENTENCE SUMMARY NEEDED HERE . See CEP style
At end . Acknowledgements ?
Water at high temperatures and pressures will be the solvent of the future
for ultrafast continuous reactions.
Using hot, compressed water as a reaction medium has been shown to increase yields
and decrease reaction times to the extent that chemical engineers will shortly be
encountering neowater on a regular basis in their work.

A familiarity with the properties of hot compressed water will soon be necessary for all
chemical engineers because it makes faster, cheaper, and cleaner chemical reaction
pathways available to industry.

Who needs a new direction ? What is neowater? Why the focus on continuous reactions?
Answers to these questions are needed because Chemical Engineers work in an applied
discipline. With both chemistry and engineering inputs, professionals must constantly be aware
of new ways of doing things as these evolve and must assess the pros and cons for a whole
range of possible applications.
The current emphasis on sustainability makes reactions in water particularly attractive to
todays practicing professionals. Not only is water ecologically friendly and low in cost, but at
high temperatures and pressures it becomes a unique and versatile reaction medium (1).
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It may be faintly recalled from elementary physical chemistry courses that, at a special critical
temperature, ordinary water becomes a new entity, being neither a liquid nor a gas. This
substance has been given the lengthy and clumsy name of supercritical water. The neater term,
neowater, is now advocated as a replacement in chemical engineering literature.
The existence of neowater was first demonstrated by Baron Charles Cagniard de la Tour nearly
200 years ago, in 1822, by rolling a flint ball back and forth within a sealed rifle barrel with one
third of the volume filled with water. This titled French engineer (Fig. 1) astutely noted that
upon heating the barrel to a certain critical temperature, the splashing sounds caused by the
movement of the flint ball within could no longer be heard. This demonstrated that the densities
of the liquid and gas phases had become equal, and the distinction between them had vanished
to form a single new phase (2-3).
Neowater constitutes a new direction for the profession because, unlike ordinary water with its
phase boundary constraints, it has been shown to behave as a powerful solvent for a broad range
of organic compounds. Together, the energy content, low viscosity, and high diffusivity as well
as the consequent superb heat and energy transfer capabilities, foretells the existence of a broad
spectrum of novel chemistries waiting to be implemented on an industrial scale.
Nevertheless, the incredible rapidity of reactions in neowater, which can take only seconds or
fractions thereof, will make conventional industrial reactors impractical and new engineering
mandatory. Continuous flow processes are clearly indicated, and two pioneering industrial
plants for the water-based conversion of biomass are currently in operation; a company named
Licella in Australia, and one named Renmatix in the USA. Their easily-accessible websites
provide additional information on the chemical engineering behind the overall processes.
However, each company pumps low-solid suspensions through reaction zones, and
consequently large volumes of water must be heated and handled. For reasons of process
economy, heat recovery presumably must be practiced. Of course, these negative aspects can be
reduced by minimizing the amount of water used. Because only a small ratio of water to
substrate is actually needed for reaction, a continuous extruder-driven process has been
developed to push wet high-solid substrates through a short, inductively-heated reaction zone
with residence times therein of only seconds (4).
The inherent attractiveness of neowater to chemical engineers as a reaction medium is that a
wide variety of properties can be achieved by varying the temperature and pressure. Once taken
beyond the critical point (374
o
C and 22 MPa), neowater can have a density similar to both
standard liquids and gases. The density can further be varied between the two, without the
cumbersome mass transfer limitations and energy inputs associated with phase transitions (5).
This makes neowater theoretically applicable to a wide range of industrial chemical processes.
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The Unique Properties of Neowater
Within the last few decades, a number of the unusual chemical properties of neowater have
been determined experimentally, several of which are of special interest to chemical engineers.
By controlling the specific pressure and temperature of neowater, the extent of hydrogen
bonding within the neowater changes, which drastically alters its chemical properties (6). In one
application of this, the excellent heat transfer capabilities of neowater have already been
extensively utilized in nuclear facilities (7).
Currently, many nuclear reactors employ what is known as a light water reactor set-up, which
utilizes a Rankine steam cycle to convert the heat generated by the reactor into additional
electrical power. However, these systems are only about 35% efficient. Alternatively, a
similarly-designed cooling system using neowater has been shown to have a thermal efficiency
of 45%, making it much more economically favorable and the object of serious study in 13
countries. Further modifications to the original design from 2003 have additionally made such a
reactor design significantly safer than current light water reactors, with faster emergency reactor
cool-down times and reducing the core damage frequency (7). The heat capacity of neowater
varies greatly depending on the temperature and pressure, but under the right conditions it can
be as much as four times higher than the heat capacity of water at standard conditions (1).
The solvent properties of neowater are also totally different from ordinary water, as evidenced
by neowaters ability to dissolve common organic compounds and a reluctance to do the same
for inorganic salts. While partly due to simple entropic favorability at high temperatures, this
solvation primarily occurs because water under standard conditions has a dielectric constant of
78.5, which is perfect for dissolving salts that also have high dielectric constants. Neowater, on
the other hand, has a much lower dielectric constant of about 10, that is in the same range as the
dielectric constants of many organic compounds (8) such as acetone. Furthermore, neowater is a
generally superior solvent because it has a much higher density than ordinary gaseous fluids,
and also has a significantly higher diffusivity than standard liquids. This makes neowater
significantly more miscible with a wider assortment of substances than competing solvents (1).
Since neowater only exists at elevated temperatures, the rates of reaction therein are vastly
accelerated by about a billion-fold relative to those observed at the boiling point of regular
water. This can also be attributed to other properties that change beyond the critical temperature
of water. With a high diffusivity and low viscosity, neowater not only increases reaction rates,
but makes them more efficient as well (5). For example, the chainlike biopolymer cellulose is
scarcely affected by boiling in water, even when exposed for several hours (9). In contrast,
cellulose in neowater is hydrolyzed into its constituent glucose monomer units with essentially
100% yield in less than one second without the presence of any catalyst whatsoever (10). The
high dielectric constant of neowater additionally lowers the activation energy of a reaction
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involving the transition to a higher polarity state. In this way, reaction rates can be carefully
controlled, by adjusting temperature and pressure in order to change the dielectric constant of
the neowater (5). Moreover, the activation energy of reactions can be lowered when the
neowater becomes part of an activation complex. An example of neowater itself acting as a
reaction catalyst is the formation of water bridge complexes as a result of the permanent dipole
of the water molecule. These complexes are reported to be critical to SN2 pathway hydrolysis
and hydrogen elimination from alcohols (5). Thus, neowater can greatly enhance existing
reaction rates and efficiencies in chemical engineering by carefully controlling the temperature
and pressure so as to create the optimum reaction medium.
In addition to the attractive physical properties of neowater, the associated chemistry is even
more exciting. For example, when an aliphatic carbon-carbon bond is thermally cleaved by the
intrinsic energy of neowater, the two radicals formed are stabilized by capture of hydrogen
atoms originating from the neowater. The recombination of such radicals into worthless char is
thereby avoided. This capture of hydrogen atoms also means that, in effect, a hydrogenation of
the cleavage fragments is simultaneously achieved in neowater without the cost of generating
elemental hydrogen gas and without the use of exotic catalysts. This remarkable and important
hydrogenation by neowater alone was elegantly demonstrated by the substitution of deuterium
oxide (D
2
O) for water in bond-splitting reactions. The cleavage fragments were then found to
contain deuterium atoms captured from the deuterium oxide (11) medium. Therefore, neowater
offers a multitude of exciting possibilities as a reaction medium because it can take on a both a
physical and a chemical role in a variety of situations.
Among these, the conversion of low-value biomass macromolecules into biofuels is of
particular promise. This is relevant to the established production of ethanol from starch, the
extractable glucose polymer in corn kernels. There are currently about 200 of such corn-based
chemical engineering facilities in the US alone. The total process is cumbersome and involves
some 13 steps from start to finish (4). Moreover, there is a major, ongoing controversy as to the
ethics of using food as a source of fuels (12). Attention is therefore being increasingly directed
to plants such as trees, grasses and beets to manufacture so-called cellulosic ethanol. These
plants consist mainly of a mixture of the polysaccharides, cellulose and hemicelluloses (about
75%) as well as the polyphenolic lignin (about 25%). Neowater can convert cellulose and
hemicelluloses of various types to simple sugars in near quantitative yield in less than a second.
Under these conditions, the aromatic rings of lignin are not degraded. When lignin is thought of
as a three-dimensional fishing net consisting of aromatic rings joined by short aliphatic chains,
neowater cuts the net between the rings to afford an oily mixture of simple phenols. After
formation from the lignin, the oil floats on the water containing the sugars from the cellulose
and the hemicelluloses.
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This breakdown of biomass into simple compounds is paralleled by the behavior of waste
synthetic plastics that are available in abundance. The most widely-used plastic, polyethylene,
is notoriously difficult to recycle economically, particularly when black in color. A great
amount, therefore, currently goes to landfills worldwide. An industrial scale, continuous
procedure for efficiently breaking down large quantities of polyethylene into fuels is a
significant chemical engineering target. Neowater technologies can do this by converting
polyethylene, and other waste plastics such as polystyrene and polypropylene, into liquid fuels
primarily in the C
2
to C
9
range (1). In contrast, the polyester, polyethylene terephthalate (PET),
quantitatively reverts to the precursors, ethylene glycol and terephthalic acid.
Conclusions
From the foregoing and the references cited, it is clear that chemical engineering in neowater
will indeed be a powerful new direction for the profession. The commercial successes of the
next decade will depend on minimizing the amount of water to be heated and this will likely
best be realized in an extruder-driven, continuous reactor.
Literature Cited
1. Marcus, Y., Supercritical Water, A Green Solvent: Properties and Uses, John Wiley &
Sons Inc., Hoboken, NJ, (2012).
2. Cagniard de la Tour, C., Expos de quelques rsultats obtenu par laction combine de la
chaleur et de la compression sur certains liquides, tels que leau, lalcool, lther sulfurique
et lessence de ptrole rectifie, Ann. Chim. Phys., 21, pp. 127-132 (1822).
3. Berche, B. et al., Critical Phenomena: 150 Years Since Cagniard de la Tour, J. Physical
Studies, 13(3), pp. 3001-3004 (2009).
4. Allan, G.G. et al., Supercritical Water Could Provide Greener Pathway to Corn Ethanol,
Ethanol Producer Magazine, 18(2), pp. 70-72 (2012).
5. Watanabe, M. et al., Chemical Reactions of C
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Compounds in Near-Critical and
Supercritical Water, Chem. Rev., 104, pp. 5803-5821 (2004).
6. Akiya, N. and P.E. Savage, Roles of Water for Chemical Reactions in High-Temperature
Water, Chem. Rev., 102, pp. 2725-2750 (2002).
7. Tsiklauri, G. et al., Supercritical Steam Cycle for Nuclear Power Plant, Nuclear Eng.
Design, 235, pp. 1651-1664 (2005).
8. Kruse, A. and E. Dinjus, Hot Compressed Water as Reaction Medium and Reactant
Properties and Synthesis Reactions, J. Supercritical Fluids, 39, pp. 362-380 (2007).
9. Allan, G.G. et al., Oligosaccharification: A New Approach to Recycling Paper-Plastic
Combinations, Cell. Chem. Tech., 40(1-2), pp. 63-70 (2006).
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10. Saka, S. and T. Ueno, Chemical Conversion of Various Celluloses to Glucose and its
Derivatives in Supercritical Water, Cellulose, 6, pp. 177-191 (1999).
11. Moriya, T. and H. Enomoto, Conversion of polyethylene to oil using supercritical water
and donation of hydrogen in supercritical water, Kobunshi Ronbunshu 58(12), pp. 661-673
(2001).
12. Dale, B., Pretreated Biomass for Food and Fuel, Ethanol Producer Magazine, 19(7), pp.
44-50 (2013).


G. GRAHAM ALLAN is now Professor of Chemical Engineering and Professor of Fiber &
Polymer Science at the University of Washington in Seattle (Phone 425 486 1649; Email;
create@uw.edu). He has authored some 300 articles and book chapters and has been awarded
72 patents on a variety of subjects. Currently his teaching emphasizes Creativity & Innovation
courses in both online and in-person versions. Previously, he taught at both the Universities of
Paisley and Strathclyde in Scotland before taking up sequential positions as research scientist
with the Du Pont and Weyerhaeuser Companies in Delaware and Washington respectively. He
is a 50 year member of the AIChE.
GREGORY M. KEGEL (Email; gmk@uw.edu) is a fourth-year undergraduate student in the
Department of Chemical Engineering at the University of Washington in Seattle. He has been
researching neowater and its potential applications for a little more than a year to date.

THOMAS E. LOOP


ACKNOWLEDGEMENTS
The assistance of Xtrudx Technology Inc. in providing access to a neowater reactor and to a
collection of related patents is gratefully appreciated.

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A typical phase diagram.
The green lines show how the freezing point can vary with pressure.
The green dotted line gives the anomalous behaviour of water.
The blue line shows how the boiling point can vary with pressure.
The red line shows the boundary where sublimation or deposition can occur.

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