378

Ind. Eng. Chem. Res. 2011, 50, 378381

Method for the Production of Deuterium-Depleted Potable Water

Feng Huang and Changgong Meng*
Department of Chemistry, Dalian UniVersity of Technology, Dalian 116024, China

A study of the utilization of dual-temperature catalytic exchange between water and hydrogen for the production
of deuterium-depleted water is presented. We use a novel catalyst with excellent physical properties for the
hot tower of the isotopic exchange. The deuterium-depleted water obtained from the experiment is in agreement
with the theoretical consideration on deuterium content at 80 C when is about 1.5. The deuterium-depleted
water with 126.3 ppm D2O is gained when is about 2 under 80 C. This kind of water can be used as
ordinary drinking water and in cosmetic and hygiene products.
1. Introduction
The exceptional properties of heavy water as a neutron
moderator make it useful in nuclear reactors. The significance
of deuterium in the nuclear industry is also well-known. Various
methods have been developed for the separation and purification
of deuterium,1-5 especially for the production of heavy water,6
such as, chemical exchange, liquid hydrogen distillation,
cryogenic adsorption, and thermal diffusion. Nevertheless,
accumulating evidence indicates that deuterium in drinking water
can be detrimental to health. For instance, there is evidence to
show that high concentration of deuterium in water (heavy
water) will cause the loss of activity and various diseases in
higher animals such as quail,9 trout,11 and others,7and in addition, some aquatic plants stop growing and developing in
heavy water.8,9
Contrarily, decreasing of the deuterium concentration will
improve the biological activity of the water. Natural water is a
mixture of H2O and D2O in which the concentration of
deuterium is approximately 150 ppm. Deuterium-depleted water
in which the concentration of deuterium is less than 80 ppm is
usually used in medical treatment. Deuterium-depleted water
with about 125 ppm deuterium is generally used in ordinary
drinking water and in the cosmetic industry.
The function of deuterium-depleted water can be divided
approximately into two aspects. First, deuterium-depleted water
could promote animal and plant growth and play a significant
role in health care. For instance, there is an increase in the rate
of photosynthesis of plants and growth promotion effects for
agricultural products and aquatic animals with use of low
deuterium water as compared to control groups using standard
water.10-13 Second, deuterium-depleted water can be applied
to cancer therapy. The daily drinking water of the patients is
replaced by deuterium-depleted water, which is administered
as an anticancer agent besides conventional therapy, and it
remarkably prolonged the survival time of the patients.14-17
Therefore, the subject of the production of deuterium-depleted
water has attracted much interest of scientists. Deuterium
enrichment and depletion are simultaneous processes. Various
technologies have been developed for the production of
deuterium poor water, such as electrolysis,18 distillation,19,20
desalination from seawater,7 and Girdler-sulfide (G-S) process.21
Separation by electrolysis is based on the difference between
the mobility coefficients of the ions. This method is very
expensive as electrolysis is a high-power consumption process.
* To whom correspondence should be addressed. Tel.: +86-41184708545. Fax: +86-411-84708545. E-mail: cgmeng@dlut.edu.cn.

Separation by distillation is based on the difference between

the boiling points of the molecules. This method uses simple
equipment and is a simple operation technology, but has highenergy consumption. Desalination from seawater by using solar
energy is an energy-saving and environment friendly method,
but it is inefficient. The G-S process is a dual-temperature
exchange method between hydrogen sulfide and water. This
process uses the very hazardous material hydrogen sulfide.
Besides these four methods, there are two processes that could
be applied for producing deuterium-depleted water. One process
is combined electrolysis and catalytic exchange (CECE). An
alternative process is bithermal hydrogen water (BHW). In each
stage there is an upper cold tower where the deuterium transfers
from the hydrogen to the liquid water, and a lower hot tower
where the deuterium transfers from the water to the hydrogen
gas.
The CECE and BHW processes rely upon hydrophobic
catalysts to catalyze the exchange reaction between hydrogen
and water. After several decades of research and development,
there are mainly three types of hydrophobic catalyst used in
the liquid-phase catalytic exchange process now, including a
Pt/C/inert carrier (Pt/C/IC),22,23 a Pt/C/polytetrafluoroethylene
(Pt/C/PTFE),24,25 and a Pt/styrene divinylbenzene copolymer
(Pt/SDB).26,27 The Pt/C/IC has high strength, good chemical
stability, and strong activity, but at the same time it has a
complex forming technique. The size and shape of the Pt/C/
PTFE are easily controlled, whereas the utilization ratio of
platinum is low. The Pt/SDB has good activity, yet it shows
low strength and small particle size. In comparison with these
three types of catalyst, our new catalyst used in this research
has higher strength, lower pressure drop, and simpler forming
technique besides basic catalytic performance.
The aim of our work is to provide an economical, efficient,
and environmental protection technique for producing deuteriumdepleted water. In this paper, we use the dual-temperature liquidphase catalytic exchange to producing deuterium-depleted water.
During the hydrogen-water isotopic exchange process, a novel
composite hydrophobic catalyst consisting of platinum directly
supported on Teflon (Pt/PTFE) is used.28 The present work
mainly focuses on the comparison between the experimental
results and the theoretical results on the deuterium concentration
of the deuterium-depleted water.
2. Methods and Materials
2.1. Experimental Flow Scheme. Figure 1 shows a schematic flow diagram of the experimental apparatus, which mainly

10.1021/ie101820f 2011 American Chemical Society

Published on Web 11/29/2010

Ind. Eng. Chem. Res., Vol. 50, No. 1, 2011

CaH2 + 2D2O ) Ca(OD)2 + 2HD

379

(1)

Figure 2 shows a simple device of the HD preparation.

3. Theoretical Background
The overall catalytic exchange of hydroen and deuterium
between liquid water and hydrogen gas consists of the following
two-step reactions:29
HDO(vapor) + H2O(liquid) S HDO(liquid) + H2O(vapor)

(2)

HD(gas) + H2O(vapor) S HDO(liquid) + H2(gas)

(3)

which totalized becomes the isotopic exchange

HD(gas) + H2O(liquid) S HDO(liquid) + H2(gas)

Figure 1. Experimental apparatus.

consists of a nitrogen gas source, a hydrogen gas source, a cold

tower, a hot tower, and some water tanks.
2.2. Preparation and Process of the Experiment. For the
isotopic exchange reaction between the hydrogen gas and the
liquid water, two types of hydrophobic catalysts have been used,
i.e., platinum on Teflon (Pt/PTFE, 3 mm long, 3 mm wide, and
1.5 mm thick) applied in the hot tower and platinum on
styrene-divinylbenzene copolymer (Pt/SDB, 2 mm sphere)
applied in the cold tower. The Pt/SDB catalyst support is
fashioned by the droplet agglomeration method, using a benzene
solution of divinylbenzene to form small spheres. The Pt/PTFE
catalyst support is formed by compression molding. Both types
of catalysts consist of 0.8 wt % Pt deposited on the catalyst
supports. The packing density of the Pt/SDB is 0.35 g mL-1,
and the packing density of the Pt/PTFE is 1.2 g mL-1.
The reactor tower is made of a Pyrex glass tube ( ) 2 cm,
l ) 60 cm). The tower is equipped with a water jacket, through
which the thermostatted water flows to maintain a constant
temperature along the tower, and a hydraulic guard is installed
at the bottom. The upper hot tower is filled with Pt/PTFE
catalyst (150 mL, 180 g), and the lower cold tower is filled
with Pt/SDB catalyst (150 mL, 53 g). The bottom and top of
both catalyst beds are packed with hydrophilic packing. The
system is initially purged with nitrogen gas to prevent hydrogen
explosion. The hydrogen gas is electrolytic hydrogen with 142
ppm D2, which is preheated in the heater and fed into the bottom
of the cold tower. The deuterated water is distilled water with
145 ppm D2O, which is fed in at the top of the cold tower and
the hot tower. The hydrogen, flowing countercurrent to the
water, passes through the catalyst bed where the isotopic
exchange takes place. The hydrogen stream is released from
the top of the hot tower and the condensed water vapor returns
to the tower.
2.3. Analysis of Deuterium Content. The deuterium content
is measured by gas chromatography (GC). For the gas phase,
the deuterium content is measured in-line by GC (STCD g 4000
mV mL mg-1). For the liquid phase, the deuterium-depleted
water with different deuterium content is converted into HD
with corresponding deuterium content by chemical reaction. The
reaction equation is as follows:

(4)

The first equation expresses the vapor-liquid equilibrium, that

is, the transfer of deuterium from water vapor to liquid water
accompanied by evaporation and condensation. The second
equation is the transfer of deuterium between hydrogen and
water vapor. The second reaction occurs only on the surface of
the catalyst, whereas the first reaction takes place at any
gas-liquid interface.
The determination of the separation factor between two
chemical species such as hydrogen and water generally requires
simultaneous analysis of both components under conditions that
do not disturb the isotopic equilibrium.
R ) x(1 - ye)/ye(1 - x)

(5)

where x is the molar fraction of deuterium in liquid phase, ye is

a molar fraction of deuterium in gas phase in equilibrium, and
R is the separation coefficient.
This procedure can be simplified when there is a large molar
excess of one component relative to the other. When the molar
fraction of deuterium in liquid phase x is very low, the ye is
expressed as
ye ) x/R

(6)

The temperature dependence is observed for all the binary

mixtures of hydrogen isotopes on the separation and purification.
The separation coefficient between hydrogen and deuterium
RH-D could obtain from an empirical formula as follows:30,31
ln RHD ) -0.1636 + 333.7/T + 33840/T2

(7)

For the two-step reaction of isotope exchange, it has been

well-known that the equilibrium constant of the transfer of
deuterium between hydrogen and water vapor increases with
decreasing temperature.30 Nevertheless, the equilibrium constant
of the vapor-liquid equilibrium decrease with decreasing temperature. Thus, there is optimal temperature in this isotope

Figure 2. HD preparation installation.

380

Ind. Eng. Chem. Res., Vol. 50, No. 1, 2011

Table 1. Chemical Parameters and Calculated Valuesa

I
II
a

pressure
(kPa)

temperature of
column (C)

hydrogen feed
(ppm D2)

hydrogen extracted
(ppm D2)

water feed
(ppm D2O)

water extracted
(ppm D2O)

101
101
101
233

30
80
30
125

3.689
2.863
3.689
2.429

142
39.3
142
39.3

39.3
50.7
39.3
59.7

145
145
145
145

247.7
133.7
247.7
124.6

Molar flow ratio of gas to water (): 1.

exchange. To enhance the separation efficiency, it is necessary

to decrease temperature without reducing the molar fraction of
water vapor.
In the course of the hydrogen-water exchange, in low
temperature, the deuterium transfers from hydrogen to water,
and in high temperature, the deuterium transfers from water to
hydrogen, and thus, to applied dual-temperature exchange to
get deuterium-depleted water.
4. Results and Discussion
4.1. Theoretical Consideration. Chemical parameters during
the liquid-phase catalytic exchange are considered to be stable
within the ranges determined by the technological process, such
as temperature, pressure, and molar flow ratio of hydrogen gas
to feedwater. The concrete data is given in Table 1. In the course
of the isotope exchange, in the cold tower, the deuterium
transfers from the hydrogen to liquid water, at the same time,
the deuterium-depleted hydrogen gas is obtained, whereas in
the hot tower, the deuterium transfers from the water to the
hydrogen gas and the deuterium-depleted water is produced.
The deuterium content of the deuterium-depleted water depends
on the deuterium content of exchange hydrogen. Thus, the
deuterium-depleted hydrogen gas from the cold tower is fed
into the bottom of the hot tower, from which the deuteriumdepleted water could be obtained.
In the process of the hydrogen-water isotopic exchange in
countercurrent, the feed gas is electrolytic hydrogen with 142
ppm D2 and the feedwater is distilled water with 145 ppm D2O.
On the basis of the mass balance,
yt - y b ) x t - x b

(8)

where y is a molar fraction of deuterium in gas phase and x is

a molar fraction of deuterium in liquid phase. The subscripts
b and t mean the bottom of the catalyst column and the
top of the catalyst column.
As the exchange reaction reaches equilibrium,
yt ) ye ) xt /R

(9)

xb ) (1 - 1/R)xt + yb

(10)

Table 2. Influence of the Molar Flow Ratio of Hydrogen Gas to

Feedwater on the Deuterium Content of the Watera
molar flow ratio
of gas to water ()

water feed
(ppm D2O)

water extracted
(ppm D2O)

1
1.5
2

145
145
145

139
132.7
126.3

a
b
c

a
Water flow rates: 24 mL h-1 for a; 18 mL h-1 for b; 12 mL h-1 for
c. The following conditions were common for all tests: Temperature of
cold tower: 30 C; temperature of hot tower: 80 C; pressure: 101 kPa;
gas flow rate: 8.6 mL s-1.

temperature of the cold tower is 30 C and the testing

temperature of the hot tower is 80 C. The deuterium concentrations of the water are shown in Table 2. The relative standard
deviation RSD % of the experimental data is less than 3%.
Data in Table 2 show that the experimental data are very
consistent with the theoretical prediction when the molar flow
ratio () is about 1.5, and the deuterium-depleted water with
126.3 ppm D2O is obtained when is about 2. Generally, in
the experimental process, the hydrogen-water exchange is not
complete. Consequently, the hydrogen-water exchange rate
increases when the hydrogen flow rate increases to a certain
value. In summary, through optimization of the experimental
conditions, the deuterium-depleted water with requisite deuterium content can be gained in the hydrogen-water isotopic
exchange process.
5. Conclusions
In this paper, a new method for the production of deuteriumdepleted potable water is successfully developed. This method
is simple and convenient, highly efficient, and an energy-saving
source. When the test conditions are reformed and adjusted,
the experimental results are in agreement with the theoretical
results. We have obtained the deuterium-depleted water with
132.7 ppm D2O when is about 1.5, and with 126.3 ppm D2O
when is about 2 at 80 C. Therefore, because of its advantages,
such as being economical, environmentally friendly, and pollution-free, this method could be applied to the industrial-scale
introduction of deuterium-depleted water.

So

In the theoretical consideration, the molar flow ratio of

hydrogen gas to feedwater () is considered as 1. In Table 1,
the chemical parameters and the calculated results are summarized.
Data in Table 1 illustrate that the deuterium content of the
water all decreases to some extent. During 30-80 C dualtemperature catalytic exchange, the deuterium content of the
water decreases from 145 to 133.7 ppm. During 30-125 C
dual-temperature catalytic exchange, the deuterium content of
the water decreases from 145 to 124.6 ppm.
4.2. Experimental Results. Considering the effect of the
temperature and the pressure on glass apparatus, the testing

Literature Cited
(1) Anil Kumar, A. V.; Jobic, H.; Bhatia, S. K. Quantum effects on
adsorption and diffusion of hydrogen and deuterium in microporous
materials. J. Phys. Chem. B 2006, 110, 1666616671.
(2) Tosti, S.; Basile, A.; Bettinali, L.; Borgognoni, F.; Gallucci, F.;
Rizzello, C. Design and process study of Pd membrane reactors. Int. J.
Hydrogen Energy 2008, 33, 50985105.
(3) Yeh, H. M. Improvement in recovery of deuterium from waterisotope mixture in concentric-tube thermal diffusion columns. Int. J.
Hydrogen Energy 2006, 31, 17561762.
(4) Dragica, L. J. S.; Scepan, S. M.; Tomislav, D. G.; Ljubica, T. P.;
Milan, M. J. Electrochemical H/D isotope separation efficiencies on Ti-Ni
intermetallic phases and alloys in relation to their hydridic and catalytic
properties. Int. J. Hydrogen Energy 2000, 25, 819823.
(5) Cristescu, I.; Cristescu, I. R.; Dorr, L.; Glugla, M.; Hellriegel, G.;
Michling, R.; et al. Commissioning of water detritiation and cryogenic

Ind. Eng. Chem. Res., Vol. 50, No. 1, 2011

distillation systems at TLK in view of ITER design. Fusion Eng. Des. 2007,
82, 21262132.
(6) Aprea, J. L. Hydrogen and hydrogen isotopes handling experience
in heavy water production and related industries. Int. J. Hydrogen Energy
2002, 27, 741752.
(7) Zlotopolski, V. M. Plant for producing low deuterium water from
sea water. U.S. Patent 2005/0109604A1, 2005.
(8) Strain, H. H.; Thomas, M. R.; Crespi, H. L.; Blake, M. I.; Katz, J. J.
Chloroplast pigments and photosynthesis in deuterated green algae. Ann.
N.Y. Acad. Sci. 1960, 84, 617633.
(9) Blake, M. I.; Crespi, H. L.; Mohan, V.; Katz, J. J. Isolation of fully
deuterated metabolites from scenedesmus obliquus grown in deuterium
oxide. J. Pharm. Sci. 1961, 50, 425429.
(10) Sinyak, Y.; Grigoriev, A.; Gaydadimov, V.; Gurieva, T.; Levinskih,
M.; Pokrovskii, B. Deuterium-free water (1H2O) in complex life-support
systems of long-term space missions. Acta Astronaut. 2003, 52, 575580.
(11) Gleason, J. D.; Friedman, I. Oats may grow better in water depleted
in oxygen-18 and deuterium. Nature 1975, 256, 305305.
(12) Pricope, F.; Stef|Abanescu; Titescu, G.; Caraus, I.; Ureche, D. Effect
of deuterium-depleted water on reproduction of rainbow trout. EnViron.
Chem. Lett. 2003, 1, 149151.
(13) Seki, K.; Usui, T. Process for promoting growth of agricultural
products and aquatic animals, and for treating pancreatic disease, involves
using deuterium-depleted water having specific deuterium concentration.
Patent JP2005328812-A, 2005.
(14) Krisztina, K.; Ildiko, S.; Gabor, S. A retrospective evaluation of
the effects of deuterium depleted water consumption on 4 patients with
brain metastases from lung cancer. Integr. Cancer Ther. 2008, 7, 172181.
(15) Marcus, I.; Farcal, L.; Pop, A.; Sevastre, B.; Duma, M.; Oros, A.
The deuterium-depleted water intake correlated with the values of some
haematological, biochemical and gravimetric parameters in NMRI mice
inoculated with a transplantable tumor. Bull. UniV. Agric. Sci. Vet. Med.
2005, 62, 172178.
(16) Manolescu, N.; Balanescu, I.; Valeca, S. C.; Traicu, R.; Marculescu,
D.; Niculita. P. In vivo determination of efficient concentration of deuterium
depleted water for cancer therapy, by administering deuterium depleted water
to animals before and after tumor grafting, and monitoring immunological
conditions in animals. Patent WO2005017522-A2, 2005.
(17) Pop, A.; Balint, E.; Manolescu, N.; Stefanescu, I.; Militaru, M. The
effect of deuterium depleted water administration on serum glycoproteins
of cytostatics treated rats. Rom. Biotechnol. Lett. 2008, 13, 7477.
(18) Laszlo, K.; Jozsef, L.; Istvan, G.; Bela, K.; Laszlo, V. Plant-scale
method for the preparation of deuterium-depleted water. Ind. Eng. Chem.
Res. 1999, 38, 24252427.
(19) Stefanescu, I.; Titescu, G.; Titescu, G. M. B. Obtaining deuterium
depleted potable water involves feeding purified water to isotopic distillation
column in presence of packing on theoretical plates and feeding reflux flow

381

on plate of superior stripping zone, with specific plate ratio. Patent

WO2006028400-A1, 2006.
(20) Stefanescu, I.; Peculea, M.; Titescu, G. Process and plant for
obtaining biologically active water depleted of deuterium - from natural
water or water from heavy water manufacture. Patent RO112422-B1, 1998.
(21) Cong, F. S. Manufacture of deuterium-depleted water for use in
pharmaceuticals, involves circulating liquid raw water between cold and
heat-exchange towers, and transferring heavy constituent in cold tower to
liquid phase by chemical exchange. Patent CN101117210-A, 2007.
(22) Li, J.; Suppiah, S.; Kutchcoskie, K. Wetproofed catalysts for
hydrogen isotope exchange. U.S. Patent 2005/0181938 A1, 2005.
(23) den Hardog, J.; Butler, J. P.; Molson, F. W. R. Ordered bed packing
module. U.S. Patent 4471014, 1984.
(24) Cristescu, I.; Cristescu, I. R.; Dorr, L.; Glugla, M.; Hellriegel, G.;
Michling, R.; et al. Commissioning of water detritiation and cryogenic
distillation systems at TLK in view of ITER design. Fusion Eng. Des. 2007,
82, 21262132.
(25) Hu, S.; Xiong, L. P.; Ren, X. B.; Wang, C. B.; Luo, Y. M. Pt-Ir
binary hydrophobic catalysts: Effects of Ir content and particle size on
catalytic performance for liquid phase catalytic exchange. Int. J. Hydrogen
Energy 2009, 34, 87238732.
(26) Paek, S.; Ahn, D. H.; Choi, H. J.; Kim, K. R.; Lee, M.; Yim, S. P.
The performance of a trickle-bed reactor packed with a Pt/SDBC catalyst
mixture for the CECE process. Fusion Eng. Des. 2007, 82, 22522258.
(27) Song, K. M.; Sohn, S. H.; Kang, D. W.; Paek, S. W.; Ahn, D. H.
Installation of liquid phase catalytic exchange columns for the Wolsong
tritium removal facility. Fusion Eng. Des. 2007, 82, 22642268.
(28) Huang, F.; Meng, C. G. Hydrophobic platinum-polytetrafluoroethylene catalyst for hydrogen isotope separation. Int. J. Hydrogen Energy
2010, 35, 61086112.
(29) Sugiyama, T.; Asakura, Y.; Uda, T.; Abe, Y.; Shiozaki, T.; Enokida,
Y.; Yamamoto, I. Preliminary experiments on hydrogen isotope separation
by watere-hydrogen chemical exchange under reduced pressure. J. Nucl.
Sci. Technol. 2004, 41, 696701.
(30) Rolston, J. H.; den Hartog, J.; Butter, J. P. The deuterium isotope
separation factor between hydrogen and liquid water. J. Phys. Chem. 1976,
80, 10641067.
(31) Andreev, B. M.; Polevoi, A. S.; Perevezentsev, A. N. Effect of
isotopic concentration on the separation coefficient of H-T, H-D and D-T
mixtures in the hydrogen-palladium system. Translation from Atom. Energ.
1978, 45, 53-58.

ReceiVed for reView August 31, 2010

ReVised manuscript receiVed October 31, 2010
Accepted November 16, 2010
IE101820F