Environment

Turning back the clock

on climate change
A technology to reverse climate change? To reduce ocean acidification? And that
also promises to increase food production? Cath O’Driscoll investigates
The oceans are already the world’s largest carbon

Claver Carroll
sink, soaking up a staggering 2bn tonnes of
carbon every year. Adding alkalis would make
them even better, by increasing the seas’ ability
to take up CO2 from the atmosphere and reducing
their ability to desorb it back (Scheme 1).

Scheme 1. Adding alkalinity to seawater

CO2 +H2O ›=H2CO3›= H+ + HCO3- ›=2H+ + CO32-

Haroon Kheshgi at Exxon Mobil suggested

adding lime (CaO), which is soluble, to seawater
in 1995 (Energy, 1995, 20, 915). However,
the idea was quickly dismissed as too energy
intensive and so costly. Producing lime involves
heating or calcining limestone [Equation 1] at
a temperature of 9000C and consumes 2.67GJ/
tonne of limestone calcined. It also generates
carbon dioxide in the process.

Equation 1
CaCO3 = CaO + CO2 Equation 1 (produces 1 mol CO2)

But Tim Kruger, a management consultant

with London firm Corven, and a Cambridge
natural sciences graduate, believes he has
a way of making the idea workable. To carry
out the process more cost-effectively, Kruger
proposes mining limestone in regions where
there is access to plenty of stranded energy,
too remote from the market to make it
economically viable.
Possible energy sources include natural gas,
that is currently flared, solar or nuclear power.
Australia’s Nullarbor Plain is a prime location
as it not only has 10 000km 3 of limestone, but
soaks up roughly 20MJ m-2 of solar irradiation
every day.

In Brief
ōThe world’s oceans currently absorb
2bn tonnes of carbon/year

ōAdding alkalis could further boost that

capacity

ōLimestone could hold the answer to

reversing climate change Nullarbor Plain, south Australia: world’s largest resource of limestone

24 Chemistry & Industry 21 July 2008


The idea has already captured the attention of
Shell, which has agreed to fund a study into its
economic feasibility. And one of the top researchers
in the field, Klaus Lackner, at Columbia University,
US, commented that it ‘is certainly worth thinking
through carefully’.
Calcium oxide added to the oceans – probably
as the pre-reacted hydroxide – reacts with carbon
dioxide dissolved in seawater to produce calcium
bicarbonate (Equation 2). The carbon dioxide from
Equation 1 can also be sequestered (see carbon
conundrum, right).
Equation 2
CaO + H2O + 2CO2 = Ca(HCO3)2 Equation 2
(absorbs 2 mol CO2)
‘This “carbon
negative” process
has the potential
to reverse the
accumulation of
carbon dioxide in the
atmosphere. It would
be possible to reduce
carbon dioxide levels
to pre-industrial
levels, without the
need to restrict
production.’
Tim Kruger, technology proponent
Crucially, for every mol of carbon dioxide
produced by calcination [Equation 1], two mols of
carbon dioxide are sequestered by the oceans.
‘This “carbon negative” process has the potential
to reverse the accumulation of carbon dioxide in the
atmosphere,’ Kruger says. ‘It would be possible to
reduce carbon dioxide levels to pre-industrial levels,
without the need to restrict production.’
In addition, the process should counter the
continued rise in ocean acidification, which
threatens marine organisms, such as molluscs,
corals and crustaceans.
Kruger estimates, for example, that ‘it would
require the consumption of approximately 5% of
the limestone in the Nullarbor Plain to return the
concentration of carbon dioxide in the atmosphere
back to pre-industrial levels’.
But while the ‘theoretical CO2 balance is roughly
right’, Lackner cautions that getting an exact figure
for the amounts of CO2 generated and absorbed by
all of these various inputs and processes is critical.
Chemistry & Industry 21 July 2008
Environment
The actual product of adding calcium oxide Carbon conundrum
to seawater is not bicarbonate but a mixture of
carbonate and bicarbonate, he notes. That makes What to do with the carbon dioxide
the multiplicative factor 1.8 mol of CO2 for every mol from the calcination reaction
of CO2 produced by calcination. Assuming stranded (Equation 1) is another problem yet
methane is used as the energy to drive the initial to be ironed out. Kruger suggests
calcination reaction, this would generate a further one option would be to use this
0.3 to 0.4 mol of CO2, so Lackner estimates the actual CO2 to grow biomass in deserts.
ratio would be 1.3–1.4 mol CO2 consumed for every Sealing the gas in an algae-filled
1.8 mol absorbed. (This gives a net 0.4–0.5 mol of water tank would promote its
CO2 sequestered, against Kruger’s own estimate of conversion to sugars and oxygen via
0.7 mol.) photosynthesis.
Sequestering the CO2 from Equation 1 would ‘Were such a system to yield 10
make the process ‘worth thinking about’, Lackner tonnes of glucose/hectare/year,
adds (see carbon conundrum, right). comparable to a conventional sugar
More worrying is the possibility that the process cane plantation, then 6 tonnes of
of bicarbonate formation could reverse to reform the water would be consumed,’ he says.
original carbonate. According to Harvard professor ‘As a single mm of rain falling on
Daniel Schrag, Lackner says, ‘the ocean will probably
shed excess limestone and thus release the CO2 in
a hectare amounts to 10 tonnes of
water, such a system could allow
what he thinks is a few hundred years. If this were the
case, then the CO2 balance becomes a bit dubious’.
the production of crops in all but the
most arid environments.’
Adding Ca(OH)2 to seawater could potentially As well as crops, the process
could be harnessed to grow biofuels.
accelerate that process, ‘partially undoing the carbon
uptake achieved’ by adding it to seawater in the first Ultimately, however, any carbon
taken up by the algae would
place, says Gideon Henderson, professor of earth
sciences at Oxford University. eventually have to be returned to
Henderson and colleagues have recently begun
investigating the environmental impacts of adding
the atmosphere, making the ‘net
carbon balance quite tenuous,’
Ca(OH)2 to seawater, including on biological
organisms. As well as determining what volumes to
Lackner points out.
A more viable option may be
use, the aim is to identify the best locations to add to sequester the CO2 by standard
techniques to entrap the gas in
alkali to seawater.
‘Uptake of CO2 could happen pretty quickly. But rocks, in aquifers and disused oil
wells. This process would be much
it depends on how the Ca(OH)2 is added, where and
in what volumes,’ he says. ‘The basic science makes cheaper than for sequestering CO2
sense but the challenge is the scale of what needs to
be done: the amount of calcite that needs digging up
from power plants, Kruger points
out, as the main costs typically
and how to put that in the oceans.’
Even assuming limestone does crash out of
involve separating the CO2 from the
other flue gases. The CO2 from the
seawater, Lackner says that the process could buy calcination route is pure.
researchers more time to develop other technologies.
‘If nothing else, one could make the argument that
there will be some peak saving right when we need
it.’
And as Shell’s Gilles Bertherin makes clear, ‘It’s a
promising idea – we are providing some early stage
funding to find out whether it can work… We have
to be sure, however, that there are no countervailing
environmental impacts of the process before we
consider taking it further.’
Kruger is developing the process in an ‘open
source’ way, and invites people to participate via a
new website: www.cquestrate.com.
Electrolysis provides the acid test
Last year, Daniel Schrag and coworkers at Harvard University reported an
alternative approach to boosting seawater alkalinity by removing hydrogen
chloride (Environ. Sci. Technol., 2007, 41, 8464). The acid is neutralised by reaction
with silicate rocks – in a process that mimics the natural weathering process,
mediated by carbonic acid in rainwater. (A similar idea is the subject of a recent
patent application by Lackner.) One drawback, however, is that the HCl needs to be
produced by electrolysis, which is potentially very costly.
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