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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


Environment

The idea has already captured the attention of The actual product of adding calcium oxide Carbon conundrum
Shell, which has agreed to fund a study into its to seawater is not bicarbonate but a mixture of
economic feasibility. And one of the top researchers carbonate and bicarbonate, he notes. That makes What to do with the carbon dioxide
in the field, Klaus Lackner, at Columbia University, the multiplicative factor 1.8 mol of CO2 for every mol from the calcination reaction
US, commented that it ‘is certainly worth thinking of CO2 produced by calcination. Assuming stranded (Equation 1) is another problem yet
through carefully’. methane is used as the energy to drive the initial to be ironed out. Kruger suggests
Calcium oxide added to the oceans – probably calcination reaction, this would generate a further one option would be to use this
as the pre-reacted hydroxide – reacts with carbon 0.3 to 0.4 mol of CO2, so Lackner estimates the actual CO2 to grow biomass in deserts.
dioxide dissolved in seawater to produce calcium ratio would be 1.3–1.4 mol CO2 consumed for every Sealing the gas in an algae-filled
bicarbonate (Equation 2). The carbon dioxide from 1.8 mol absorbed. (This gives a net 0.4–0.5 mol of water tank would promote its
Equation 1 can also be sequestered (see carbon CO2 sequestered, against Kruger’s own estimate of conversion to sugars and oxygen via
conundrum, right). 0.7 mol.) photosynthesis.
Sequestering the CO2 from Equation 1 would ‘Were such a system to yield 10
Equation 2 make the process ‘worth thinking about’, Lackner tonnes of glucose/hectare/year,
CaO + H2O + 2CO2 = Ca(HCO3)2 Equation 2 adds (see carbon conundrum, right). comparable to a conventional sugar
(absorbs 2 mol CO2) 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
‘This “carbon 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
negative” process 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.’
has the potential 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
to reverse the uptake achieved’ by adding it to seawater in the first Ultimately, however, any carbon
taken up by the algae would
accumulation of place, says Gideon Henderson, professor of earth
sciences at Oxford University. eventually have to be returned to
carbon dioxide in the Henderson and colleagues have recently begun
investigating the environmental impacts of adding
the atmosphere, making the ‘net
carbon balance quite tenuous,’
atmosphere. It would 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
be possible to reduce 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.
carbon dioxide levels ‘Uptake of CO2 could happen pretty quickly. But rocks, in aquifers and disused oil
wells. This process would be much
to pre-industrial 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
levels, without the 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
need to restrict 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
production.’ seawater, Lackner says that the process could buy calcination route is pure.
researchers more time to develop other technologies.
Tim Kruger, technology proponent ‘If nothing else, one could make the argument that
there will be some peak saving right when we need
it.’
Crucially, for every mol of carbon dioxide And as Shell’s Gilles Bertherin makes clear, ‘It’s a
produced by calcination [Equation 1], two mols of promising idea – we are providing some early stage
carbon dioxide are sequestered by the oceans. funding to find out whether it can work… We have
‘This “carbon negative” process has the potential to be sure, however, that there are no countervailing
to reverse the accumulation of carbon dioxide in the environmental impacts of the process before we
atmosphere,’ Kruger says. ‘It would be possible to consider taking it further.’
reduce carbon dioxide levels to pre-industrial levels, Kruger is developing the process in an ‘open
without the need to restrict production.’ source’ way, and invites people to participate via a
In addition, the process should counter the new website: www.cquestrate.com.
continued rise in ocean acidification, which
threatens marine organisms, such as molluscs,
corals and crustaceans. Electrolysis provides the acid test
Kruger estimates, for example, that ‘it would
require the consumption of approximately 5% of Last year, Daniel Schrag and coworkers at Harvard University reported an
the limestone in the Nullarbor Plain to return the alternative approach to boosting seawater alkalinity by removing hydrogen
concentration of carbon dioxide in the atmosphere chloride (Environ. Sci. Technol., 2007, 41, 8464). The acid is neutralised by reaction
back to pre-industrial levels’. with silicate rocks – in a process that mimics the natural weathering process,
But while the ‘theoretical CO2 balance is roughly mediated by carbonic acid in rainwater. (A similar idea is the subject of a recent
right’, Lackner cautions that getting an exact figure patent application by Lackner.) One drawback, however, is that the HCl needs to be
for the amounts of CO2 generated and absorbed by produced by electrolysis, which is potentially very costly.
all of these various inputs and processes is critical.

Chemistry & Industry 21 July 2008 25