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Wednesday, February 18, 2015

Carbon capture and storage



From Wikipedia, the free encyclopedia


Schematic showing both terrestrial and geological sequestration of carbon dioxide emissions from a coal-fired plant

Carbon capture and storage (CCS) (or carbon capture and sequestration) is the process of capturing waste carbon dioxide (CO
2
) from large point sources, such as fossil fuel power plants, transporting it to a storage site, and depositing it where it will not enter the atmosphere, normally an underground geological formation. The aim is to prevent the release of large quantities of CO
2
into the atmosphere (from fossil fuel use in power generation and other industries). It is a potential means of mitigating the contribution of fossil fuel emissions to global warming[1] and ocean acidification.[2] Although CO
2
has been injected into geological formations for several decades for various purposes, including enhanced oil recovery, the long term storage of CO
2
is a relatively new concept. The first commercial example was Weyburn in 2000.[3] 'CCS' can also be used to describe the scrubbing of CO
2
from ambient air as a climate engineering technique.

An integrated pilot-scale CCS power plant was to begin operating in September 2008 in the eastern German power plant Schwarze Pumpe run by utility Vattenfall, in the hope of answering questions about technological feasibility and economic efficiency. CCS applied to a modern conventional power plant could reduce CO
2
emissions to the atmosphere by approximately 80–90% compared to a plant without CCS.[4] The IPCC estimates that the economic potential of CCS could be between 10% and 55% of the total carbon mitigation effort until year 2100.[4]

Capturing and compressing CO
2
may increase the fuel needs of a coal-fired CCS plant by 25–40%.[4] These and other system costs are estimated to increase the cost of the energy produced by 21–91% for purpose built plants.[4] Applying the technology to existing plants would be more expensive especially if they are far from a sequestration site. Recent industry reports suggest that with successful research, development and deployment (RD&D), sequestered coal-based electricity generation in 2025 may cost less than unsequestered coal-based electricity generation today.[5]

Storage of the CO
2
is envisaged either in deep geological formations, or in the form of mineral carbonates. Deep ocean storage is no longer considered feasible because it greatly increases the problem of ocean acidification.[6] Geological formations are currently considered the most promising sequestration sites. The National Energy Technology Laboratory (NETL) reported that North America has enough storage capacity for more than 900 years worth of carbon dioxide at current production rates.[7] A general problem is that long term predictions about submarine or underground storage security are very difficult and uncertain, and there is still the risk that CO
2
might leak into the atmosphere.[8]

Capture

Capturing CO
2
is probably most effective at point sources, such as large fossil fuel or biomass energy facilities, industries with major CO
2
emissions, natural gas processing, synthetic fuel plants and fossil fuel-based hydrogen production plants. Extraction (recovery) from air is possible, but not very practical. The CO
2
concentration drops rapidly moving away from the point source. The lower concentration increases the amount of mass flow that must be processed (per tonne of carbon dioxide extracted).[9]

Concentrated CO
2
from the combustion of coal in oxygen is relatively pure, and could be directly processed. Impurities in CO
2
streams could have a significant effect on their phase behaviour and could pose a significant threat of increased corrosion of pipeline and well materials.[10] In instances where CO
2
impurities exist and especially with air capture, a scrubbing process would be needed.[11]

Organisms that produce ethanol by fermentation generate cool, essentially pure CO
2
that can be pumped underground.[12] Fermentation produces slightly less CO
2
than ethanol by weight.
Broadly, three different types of technologies for scrubbing exist: post-combustion, pre-combustion, and oxyfuel combustion:
  • In post combustion capture, the CO
    2
    is removed after combustion of the fossil fuel — this is the scheme that would be applied to fossil-fuel burning power plants. Here, carbon dioxide is captured from flue gases at power stations or other large point sources. The technology is well understood and is currently used in other industrial applications, although not at the same scale as might be required in a commercial scale power station.
  • The technology for pre-combustion is widely applied in fertilizer, chemical, gaseous fuel (H2, CH4), and power production.[13] In these cases, the fossil fuel is partially oxidized, for instance in a gasifier. The resulting syngas (CO and H2) is shifted into CO
    2
    and H2. The resulting CO
    2
    can be captured from a relatively pure exhaust stream. The H2 can now be used as fuel; the carbon dioxide is removed before combustion takes place. There are several advantages and disadvantages when compared to conventional post combustion carbon dioxide capture.[14][15] The CO
    2
    is removed after combustion of fossil fuels, but before the flue gas is expanded to atmospheric pressure. This scheme is applied to new fossil fuel burning power plants, or to existing plants where re-powering is an option. The capture before expansion, i.e. from pressurized gas, is standard in almost all industrial CO
    2
    capture processes, at the same scale as will be required for utility power plants.[16][17]
  • In oxy-fuel combustion[18] the fuel is burned in oxygen instead of air. To limit the resulting flame temperatures to levels common during conventional combustion, cooled flue gas is recirculated and injected into the combustion chamber. The flue gas consists of mainly carbon dioxide and water vapour, the latter of which is condensed through cooling. The result is an almost pure carbon dioxide stream that can be transported to the sequestration site and stored. Power plant processes based on oxyfuel combustion are sometimes referred to as "zero emission" cycles, because the CO
    2
    stored is not a fraction removed from the flue gas stream (as in the cases of pre- and post-combustion capture) but the flue gas stream itself. A certain fraction of the CO
    2
    generated during combustion will inevitably end up in the condensed water. To warrant the label "zero emission" the water would thus have to be treated or disposed of appropriately. The technique is promising, but the initial air separation step demands a lot of energy.
An alternate method under development is chemical looping combustion (CLC). Chemical looping uses a metal oxide as a solid oxygen carrier. Metal oxide particles react with a solid, liquid or gaseous fuel in a fluidized bed combustor, producing solid metal particles and a mixture of carbon dioxide and water vapor. The water vapor is condensed, leaving pure carbon dioxide, which can then be sequestered. The solid metal particles are circulated to another fluidized bed where they react with air, producing heat and regenerating metal oxide particles that are recirculated to the fluidized bed combustor. A variant of chemical looping is calcium looping, which uses the alternating carbonation and then calcination of a calcium oxide based carrier as a means of capturing CO
2
.[19]

A few engineering proposals have been made for the more difficult task of capturing CO
2
directly from the air, but work in this area is still in its infancy. Capture costs are estimated to be higher than from point sources, but may be feasible for dealing with emissions from diffuse sources such as automobiles and aircraft.[20] The theoretically required energy for air capture is only slightly more than for capture from point sources. The additional costs come from the devices that use the natural air flow. Global Research Technologies demonstrated a pre-prototype of air capture technology in 2007.[21]

Removing CO
2
from the atmosphere
is a form of climate engineering by greenhouse gas remediation. Some media reports[citation needed] have suggested that techniques of this type, if coupled with effective carbon sequestration technologies, may offer a comprehensive solution to global warming.

It is more usual to see such techniques proposed for air capture, than for flue gas treatment. Carbon dioxide capture and storage is more commonly proposed on plants burning coal in oxygen extracted from the air, which means the CO
2
is highly concentrated and no scrubbing process is necessary. According to the Wallula Energy Resource Center in Washington state, by gasifying coal, it is possible to capture approximately 65% of carbon dioxide embedded in it and sequester it in a solid form.[22]

Transport

After capture, the CO
2
would have to be transported to suitable storage sites. This is done by pipeline, which is generally the cheapest form of transport. In 2008, there were approximately 5,800 km of CO
2
pipelines in the United States, used to transport CO
2
to oil production fields where it is then injected into older fields to extract oil. The injection of CO
2
to produce oil is generally called Enhanced Oil Recovery or EOR.[citation needed] In addition, there are several pilot programs in various stages to test the long-term storage of CO
2
in non-oil producing geologic formations.

According to the Congressional Research Service, "There are important unanswered questions about pipeline network requirements, economic regulation, utility cost recovery, regulatory classification of CO
2
itself, and pipeline safety. Furthermore, because CO
2
pipelines for enhanced oil recovery are already in use today, policy decisions affecting CO
2
pipelines take on an urgency that is unrecognized by many. Federal classification of CO
2
as both a commodity (by the Bureau of Land Management) and as a pollutant (by the Environmental Protection Agency) could potentially create an immediate conflict which may need to be addressed not only for the sake of future CCS implementation, but also to ensure consistency of future CCS with CO
2
pipeline operations today."[23][24]

Ships could also be utilized for transport where pipelines are not feasible. These methods are currently used for transporting CO
2
for other applications.

Sequestration

Various forms have been conceived for permanent storage of CO2. These forms include gaseous storage in various deep geological formations (including saline formations and exhausted gas fields), and solid storage by reaction of CO2 with metal oxides to produce stable carbonates.

Geological storage

Also known as geo-sequestration, this method involves injecting carbon dioxide, generally in supercritical form, directly into underground geological formations. Oil fields, gas fields, saline formations, unmineable coal seams, and saline-filled basalt formations have been suggested as storage sites. Various physical (e.g., highly impermeable caprock) and geochemical trapping mechanisms would prevent the CO
2
from escaping to the surface.[25]

CO
2
is sometimes injected into declining oil fields to increase oil recovery. Approximately 30 to 50 million metric tonnes of CO
2
are injected annually in the United States into declining oil fields.[26] This option is attractive because the geology of hydrocarbon reservoirs is generally well understood and storage costs may be partly offset by the sale of additional oil that is recovered.[27] Disadvantages of old oil fields are their geographic distribution and their limited capacity, as well as the fact that subsequent burning of the additional oil recovered will offset much or all of the reduction in CO
2
emissions.[28]

Unmineable coal seams can be used to store CO
2
because the CO
2
molecules attach to the surface of coal. The technical feasibility, however, depends on the permeability of the coal bed. In the process of absorption the coal releases previously absorbed methane, and the methane can be recovered (enhanced coal bed methane recovery). The sale of the methane can be used to offset a portion of the cost of the CO
2
storage. Burning the resultant methane, however, would negate some of the benefit of sequestering the original CO
2
.

Saline formations contain highly mineralized brines, and have so far been considered of no benefit to humans. Saline aquifers have been used for storage of chemical waste in a few cases. The main advantage of saline aquifers is their large potential storage volume and their common occurrence. The major disadvantage of saline aquifers is that relatively little is known about them, especially compared to oil fields. To keep the cost of storage acceptable, the geophysical exploration may be limited, resulting in larger uncertainty about the aquifer structure. Unlike storage in oil fields or coal beds, no side product will offset the storage cost. Leakage of CO
2
back into the atmosphere may be a problem in saline aquifer storage. Current research shows, however, that trapping mechanisms such as structural trapping, residual trapping, solubility trapping and mineral trapping could immobilize the CO
2
underground and reduce the risk of leakage.[25]

Enhanced oil recovery

Enhanced oil recovery (EOR) is a generic term for techniques used to increase the amount of crude oil that can be extracted from an oil field. In Carbon Capture & Sequestration Enhanced Oil Recovery (CCS EOR), carbon dioxide is injected into an oil field to recover oil that is often never recovered using more traditional methods.

Crude oil development and production in U.S. oil reservoirs can include up to three distinct phases: primary, secondary, and tertiary (or enhanced) recovery.[29] During primary recovery only about 10 percent of a reservoir's original oil in place is typically produced. Secondary recovery techniques extend a field's productive life generally by injecting water or gas to displace oil and drive it to a production wellbore, resulting in the recovery of 20 to 40 percent of the original oil in place. However, with much of the easy-to-produce oil already recovered from U.S. oil fields, producers have attempted several tertiary, or enhanced oil recovery (EOR), techniques that offer prospects for ultimately producing 30 to 60 percent, or more, of the reservoir's original oil in place.[30]

An example of a project that will use CCS EOR is the Kemper Project in Mississippi. Due to the Kemper Project's close proximity to oil fields, the carbon dioxide byproduct from producing electricity will be transported to the neighboring oil fields for EOR.[31]

Ocean storage

In the past, it was suggested that CO
2
could be stored in the oceans, but this would only exacerbate ocean acidification and has been made illegal under specific regulations. Ocean storage is no longer considered feasible.[6]

Mineral storage

In this process, CO
2
is exothermically reacted with available metal oxides, which in turn produces stable carbonates. This process occurs naturally over many years and is responsible for a great amount of surface limestone. The idea of using Olivine has been promoted by the geochemist Prof. Schuiling.[32] The reaction rate can be made faster, for example, with a catalyst[33] or by reacting at higher temperatures and/or pressures, or by pre-treatment of the minerals, although this method can require additional energy. The IPCC estimates that a power plant equipped with CCS using mineral storage will need 60–180% more energy than a power plant without CCS.[4]

The economics of mineral carbonation at scale are now being tested in a world-first pilot plant project based in Newcastle, Australia. New techniques for mineral activation and reaction have been developed the GreenMag Group and the University of Newcastle and funded by the New South Wales and Australian Governments to be operational by 2013.[34]

In 2009 it was reported that scientists had mapped 6,000 square miles (16,000 km2) of rock formations in the U.S. that could be used to store 500 years' worth of U.S. carbon dioxide emissions.[35] A study on mineral sequestration in the US states:
Carbon sequestration by reacting naturally occurring Mg and Ca containing minerals with CO
2
to form carbonates has many unique advantages. Most notabl[e] is the fact that carbonates have a lower energy state than CO
2
, which is why mineral carbonation is thermodynamically favorable and occurs naturally (e.g., the weathering of rock over geologic time periods). Secondly, the raw materials such as magnesium based minerals are abundant. Finally, the produced carbonates are unarguably stable and thus re-release of CO
2
into the atmosphere is not an issue. However, conventional carbonation pathways are slow under ambient temperatures and pressures. The significant challenge being addressed by this effort is to identify an industrially and environmentally viable carbonation route that will allow mineral sequestration to be implemented with acceptable economics.[36]
The following table lists principal metal oxides of Earth's Crust. Theoretically, up to 22% of this mineral mass is able to form carbonates.

Earthen Oxide Percent of Crust Carbonate Enthalpy change (kJ/mol)
SiO2 59.71
Al2O3 15.41
CaO 4.90 CaCO3 -179
MgO 4.36 MgCO3 -118
Na2O 3.55 Na2CO3 -322
FeO 3.52 FeCO3 -85
K2O 2.80 K2CO3 -393.5
Fe2O3 2.63 FeCO3 112
21.76 All Carbonates

Ultramafic mine tailings are a readily available source of fine-grained metal oxides that can act as artificial carbon sinks to reduce net greenhouse gas emissions in the mining industry.[37] Accelerating passive CO2 sequestration via mineral carbonation may be achieved through microbial processes that enhance mineral dissolution and carbonate precipitation.[38][39][40]

Energy requirements

The energy requirements of sequestration processes may be significant. In one paper, sequestration consumed 25 percent of the plant's rated 600 megawatt output capacity.[41]
After adding CO
2
capture and compression, the capacity of the coal-fired power plant is reduced to 457 MW.

Leakage


Lake Nyos as it appeared fewer than two weeks after the eruption; August 29, 1986.

A major concern with CCS is whether leakage of stored CO
2
will compromise CCS as a climate change mitigation option. For well-selected, designed and managed geological storage sites, IPCC estimates that risks are comparable to those associated with current hydrocarbon activity.[42] Although some question this assumption as arbitrary citing a lack of experience in such long term storage.[43][44] CO
2
could be trapped for millions of years, and although some leakage occurs upwards through the soil, well selected storage sites are likely to retain over 99% of the injected CO
2
over 1000 years.[45] Leakage through the injection pipe is a greater risk.[46]

Although the injection pipe is usually protected with non-return valves to prevent release on a power outage, there is still a risk that the pipe itself could tear and leak due to the pressure. The Berkel en Rodenrijs incident in December 2008 was an example, where a modest release of CO
2
from a pipeline under a bridge resulted in the deaths of some ducks sheltering there.[47] In order to measure accidental carbon releases more accurately and decrease the risk of fatalities through this type of leakage, the implementation of CO
2
alert meters around the project perimeter has been proposed. Malfunction of a carbon dioxide industrial fire suppression system in a large warehouse released CO
2
and 14 citizens collapsed on the nearby public road. A release of CO
2
from a salt mine killed a person at distance of 300 meters.[48]

In 1986 a large leakage of naturally sequestered CO
2
rose from Lake Nyos in Cameroon and asphyxiated 1,700 people. While the carbon had been sequestered naturally, some point to the event as evidence for the potentially catastrophic effects of sequestering carbon artificially.[49] The Lake Nyos disaster resulted from a volcanic event, which very suddenly released as much as a cubic kilometre of CO
2
gas from a pool of naturally occurring CO
2
under the lake in a deep narrow valley. The location of this pool of CO
2
is not a place where man can inject or store CO
2
, and this pool was not known about nor monitored until after the occurrence of the natural disaster.

For ocean storage, the retention of CO
2
would depend on the depth. The IPCC estimates 30–85% of the sequestered carbon dioxide would be retained after 500 years for depths 1000–3000 m. Mineral storage is not regarded as having any risks of leakage. The IPCC recommends that limits be set to the amount of leakage that can take place. This might rule out deep ocean storage as an option.

At the conditions of the deeper oceans, (about 400 bar or 40 MPa, 280 K) water–CO
2
(l) mixing is very low (where carbonate formation/acidification is the rate limiting step), but the formation of water-CO
2
hydrates, a kind of solid water cage that surrounds the CO
2
, is favorable.

To further investigate the safety of CO
2
sequestration, Norway's Sleipner gas field can be studied, as it is the oldest plant that stores CO
2
on an industrial scale. According to an environmental assessment of the gas field which was conducted after ten years of operation, the author affirmed that geosequestration of CO
2
was the most definite form of permanent geological storage of CO
2
:
Available geological information shows absence of major tectonic events after the deposition of the Utsira formation [saline reservoir]. This implies that the geological environment is tectonically stable and a site suitable for carbon dioxide storage. The solubility trapping [is] the most permanent and secure form of geological storage.[50]
In March 2009 StatoilHydro issued a study showing the slow spread of CO
2
in the formation after more than 10 years operation.[51]

Phase I of the Weyburn-Midale Carbon Dioxide Project in Weyburn, Saskatchewan, Canada has determined that the likelihood of stored CO
2
release is less than one percent in 5,000 years.[52] A January 2011 report, however, claimed evidence of leakage in land above that project.[53] This report was strongly refuted by the IEAGHG Weyburn-Midale CO
2
Monitoring and Storage Project, which issued an eight page analysis of the study, claiming that it showed no evidence of leakage from the reservoir.[54]

The liability of potential leak(s) is one of the largest barriers to large-scale CCS. To assess and reduce such liability, the leakage of stored gasses, particularly carbon dioxide, into the atmosphere may be detected via atmospheric gas monitoring, and can be quantified directly via the eddy covariance flux measurements,[55][56][57]

Carbon dioxide recycling / Carbon Capture and Utilization (CCU)

Recycling CO
2
may offer a response to the global challenge of significantly reducing greenhouse gas emissions from major stationary (industrial) emitters in the near to medium term,[citation needed] but is usually considered a different technological category from CCS.[58] Technologies under development, such as Bio CCS Algal Synthesis,[59] utilises pre-smokestack CO
2
(such as from a coal-fired power station) as a useful feedstock input to the production of oil-rich algae in solar membranes to produce oil for plastics and transport fuel (including aviation fuel), and nutritious stock-feed for farm animal production.[59] The CO
2
and other captured greenhouse gases are injected into the membranes containing waste water and select strains of algae causing, together with sunlight or UV light, an oil rich biomass that doubles in mass every 24 hours[citation needed].

The Bio CCS Algal Synthesis process is based on earth science photosynthesis: the technology is entirely retrofittable and collocated with the emitter, and the capital outlays may offer a return upon investment due to the high value commodities produced (oil for plastics, fuel and feed).

Bio CCS Algal Synthesis test facilities are being trialed at Australia's three largest coal-fired power stations (Tarong, Queensland; Eraring, NSW; Loy Yang, Victoria) using piped pre-emission smokestack CO
2
(and other greenhouse gases) as feedstock to grow oil-rich algal biomass in enclosed membranes for the production of plastics, transport fuel and nutritious animal feed.

Another potentially useful way of dealing with industrial sources of CO
2
is to convert it into hydrocarbons where it can be stored or reused as fuel or to make plastics. There are a number of projects investigating this possibility.[60]

Carbon dioxide scrubbing variants exist based on potassium carbonate which can be used to create liquid fuels, though this process requires a great deal of energy input.[61] Although the creation of fuel from atmospheric CO
2
is not a climate engineering technique, nor does it actually function as greenhouse gas remediation, it nevertheless is potentially useful in the creation of a low carbon economy.

Other uses are the production of stable carbonates from silicates (i.e. Olivine produces Magnesium carbonate. This process is still in the R&D phase.[62]

Single step methods: methanol

A proven process to produce a hydrocarbon is to make methanol. Methanol is rather easily synthesized from CO
2
and H2 (See Green Methanol Synthesis). Based on this fact the idea of a methanol economy was born.

Single step methods: hydrocarbons

At the department of Industrial Chemistry and Engineering of Materials at the University of Messina, Italy, there is a project to develop a system which works like a fuel-cell in reverse, whereby a catalyst is used that enables sunlight to split water into hydrogen ions and oxygen gas. The ions cross a membrane where they react with the CO
2
to create hydrocarbons.[63]

Two step methods

If CO
2
is heated to 2400 °C, it splits into carbon monoxide (CO) and oxygen. The Fischer-Tropsch process can then be used to convert the CO into hydrocarbons. The required temperature can be achieved by using a chamber containing a mirror to focus sunlight on the gas. Rival teams are developing such chambers, at Solarec and at Sandia National Laboratories, both based in New Mexico.[64] According to Sandia these chambers could provide enough fuel to power 100% of domestic vehicles using 5800 km2; unlike biofuels this would not take fertile land away from crops but would be land that is not being used for anything else. James May, the British TV presenter, visited a demonstration plant in a programme in his 'Big Ideas' series.

Example CCS projects

Industrial-scale projects

As at September 2012, the Global CCS Institute identified 75 large-scale integrated projects in its 2012 Global Status of CCS report[65] which is a net increase of one project since its 2011 Global Status of CCS report. 16 of these projects are in operation or in construction capturing around 36 million tonnes of CO
2
per annum.[65][66] For more information see Integrated CCS Projects[67] on the Global CCS Institute's website. For information on EU projects see Zero Emissions Platform[68] website. The eight large-scale integrated CCS projects currently in operation are:

1. In Salah CO
2
Injection — Algeria

In Salah is a fully operational onshore gas field with CO
2
injection. CO
2
is separated from produced gas and reinjected in the producing hydrocarbon reservoir zones. Since 2004, about 1 Mt/a of CO
2
has been captured during natural gas extraction and injected into the Krechba geologic formation at a depth of 1,800m. The Krechba formation is expected to store 17Mt CO
2
over the life of the project.

2. Sleipner CO
2
Injection — Norway

Sleipner[51] is a fully operational offshore gas field with CO2 injection initiated in 1996. CO2 is separated from produced gas and reinjected in the Utsira saline aquifer (800–1000 m below ocean floor) above the hydrocarbon reservoir zones. This aquifer extends much further north from the Sleipner facility at its southern extreme. The large size of the reservoir accounts for why 600 billion tonnes of CO2 are expected to be stored, long after the Sleipner natural gas project has ended.

3. Snøhvit CO
2
Injection — Norway

Snøhvit is a fully operational offshore gas field with CO
2
injection. The LNG plant is located onshore. CO
2
is necessarily separated to produce liquefied natural gas (LNG) and then CO
2
is injected in a saline aquifer below the hydrocarbon reservoir zones offshore at a rate of 700,000 t/a into the Tubåen sandstone formation 2,600 m under the seabed for storage. This formation was closed

April 2011, and injection started in the Stø-formation where produced gas is taken. Produced CO
2
is increasing, therefore separation capacity may limit production before end 2015 when a new formation will be drilled for CO
2
-injection only. (Teknisk Ukeblad nr. 30, 2013, tu.no)

4. Great Plains Synfuel Plant and Weyburn-Midale Project — Canada

Weyburn-Midale is a coal gasification operation that produces synthetic natural gas and various petrochemicals from coal. This project captures about 2.8 Mt/a of CO
2
from its coal gasification plant located in North Dakota, USA, transported by pipeline 320 km across the Canadian border and injects it into depleting oil fields in Saskatchewan where it is used for enhanced oil recovery (EOR).

5. Shute Creek Gas Processing Facility — USA

Around 7 million tonnes per annum of carbon dioxide are recovered from ExxonMobil's Shute Creek gas processing plant in Wyoming, and transported by pipeline to various oil fields for enhanced oil recovery. This project has been operational since 1986.

6. Enid Fertilizer — USA

The Enid Fertilizer plant sends 675,000 tonnes of CO
2
to be used for EOR. The pipeline and wells are operated separately by Anadarko Petroleum.

7. Val Verde Natural Gas Plants — USA

CO
2
from Mitchell, Gray Ranch, Puckett, and Turrell gas processing plants is transported via the Val Verde and CRC pipelines[where?] for EOR (incl. Sharon Ridge[clarification needed] EOR field).[citation needed]

8. Century Plant — USA

Occidental Petroleum, along with Sandridge Energy, is operating a West Texas hydrocarbon gas processing plant and related pipeline infrastructure that provides CO2 for use in EOR. With a total CO2 capture capacity of 8.5 Mt/a expected in 2012, the Century plant would be the largest single industrial source CO
2
capture facility in North America.

Canada

The federal government in the 2008 and 2009 budgets has invested approximately $1.4 billion in Carbon Capture and Storage development.[69]

Alberta

Alberta has committed $170 million in 2013/2014 – and a total of $1.3 billion over 15 years – to fund two large-scale CCS projects that will help reduce CO
2
emissions from oil sands refining.[70] In 2010 a grant agreement was signed with the Alberta Carbon Trunk Line.[71] The second is the Quest Project.[72]

British Columbia

Spectra Energy's Fort Nelson Project is proposed but still needs to secure funding.[73]

Saskatchewan

Led by the province's full-service utility, SaskPower, one of the world's first and largest full production carbon capture facilities is operating at Boundary Dam Power Station. With an initial investment of $1.5 to $1.6 billion,[74] SaskPower will be generating a revenue by selling a portion of the captured CO
2
back into the market to be used for enhanced oil recovery. The project started in May 2011 and became operational in October 2014.[75] The post-combustion full flue gas capture process will capture 1 million tonnes of CO
2
a year.[73]

Pilot Projects

The Alberta Saline Aquifer Project (ASAP), Husky Upgrader and Ethanol Plant pilot, Heartland Area Redwater Project (HARP), Wabamun Area Sequestration Project(WASP), and Aquistore.[76]

Another Canadian initiative is the Integrated CO
2
Network (ICO
2
N), a group of industry participants providing a framework for carbon capture and storage development in Canada.[77] Other Canadian organizations related to CCS include CCS 101, Carbon Management Canada, IPAC CO
2
, and the Canadian Clean Power Coalition.[78]

Netherlands

In the Netherlands, a 68 megawatt oxyfuel plant ("Zero Emission Power Plant") was being planned to be operational in 2009.[79] This project was later canceled.

ROAD (Rotterdam Capture and Storage Demonstration project) is a joint project by E.ON Benelux and Electrabel Nederland / GDF SUEZ Group. Every year, starting in 2015 ROAD will capture around 1.1 million tonnes of CO
2
at the new power plant on the Maasvlakte. This will be stored in depleted gas reservoirs under the North Sea.[80]

Developed in the Netherlands, an electrocatalysis by a copper complex helps reduce carbon dioxide to oxalic Acid.[81]

Norway

In Norway, the CO
2
Technology Centre (TCM) at Mongstad began construction in 2009, and completed in 2012. It includes two capture technology plants (one advanced amine and one chilled ammonia), both capturing fluegas from two sources. This includes a gas-fired power plant and refinery cracker fluegas (similar to coal-fired power plant fluegas).

In addition to this, the Mongstad site was also planned to have a full-scale CCS demonstration plant. The project was delayed to 2014, 2018, and then indefinitely.[82] The project cost rose to USD 985 million.[83] Then in October 2011, Aker Solutions' wrote off its investment in Aker Clean Carbon, declaring the carbon sequestration market to be "dead".[84]

On 1 October 2013 Norway asked Gassnova not to sign any contracts for Carbon capture and storage outside Mongstad.[85]

Poland

In Belchatów, Poland,[86] a lignite-fired energy plant of more than 858 MW is planned to be in operation in 2013.[87][88]

United States

In October 2007, the Bureau of Economic Geology at the University of Texas at Austin received a 10-year, $38 million subcontract to conduct the first intensively monitored long-term project in the United States studying the feasibility of injecting a large volume of CO
2
for underground storage.[89] The project is a research program of the Southeast Regional Carbon Sequestration Partnership (SECARB), funded by the National Energy Technology Laboratory of the U.S. Department of Energy (DOE).

The SECARB partnership will demonstrate CO
2
injection rate and storage capacity in the Tuscaloosa-Woodbine geologic system that stretches from Texas to Florida. The region has the potential to store more than 200 billion tons[vague] of CO
2
from major point sources in the region, equal to about 33 years of overall U.S. emissions at present rates. Beginning in fall 2007, the project will inject CO
2
at the rate of one million tons[vague] per year, for up to 1.5 years, into brine up to 10,000 feet (3,000 m) below the land surface near the Cranfield oil field, which lays about 15 miles (24 km) east of Natchez, Mississippi. Experimental equipment will measure the ability of the subsurface to accept and retain CO
2
.

Currently, the United States government has approved the construction of what is touted as the world's first CCS power plant, FutureGen. On January 29, 2008, however, the Department of Energy announced it was recasting the FutureGen project, and, on June 24, 2008, DoE published a funding opportunity announcement seeking proposals for an IGCC project, with integrated CCS, of at least 250MW.[90] In 2013 and 2013, the FutureGen Alliance proposed a new location in Morgan County, Illinois as an underground storage location for carbon dioxide captured from a power plant retrofitted for oxy-fuel combustion of coal. The liquified carbon dioxide would be transported through about 30 miles of pipeline and injected into four underground injection wells.[91][92]

Examples of carbon sequestration at an existing US coal plant can be found at utility company Luminant's pilot version at its Big Brown Steam Electric Station in Fairfield, Texas. This system is converting carbon from smokestacks into baking soda. Skyonic plans to circumvent storage problems of liquid CO
2
by storing baking soda in mines, landfills, or simply to be sold as industrial or food grade baking soda.[93] Green Fuel Technologies is piloting and implementing algae based carbon capture, circumventing storage issues by then converting algae into fuel or feed.[94]

In November 2008, the DOE awarded a $66.9 million eight-year grant to a research partnership headed by Montana State University to demonstrate that underground geologic formations "can store huge volumes of carbon dioxide economically, safely and permanently".[citation needed] Researchers under the Big Sky Regional Carbon Sequestration Project plan to inject up to one million tonnes of CO
2
into sandstone beneath southwestern Wyoming.[95]

In the United States, four different synthetic fuel projects are moving forward, which have publicly announced plans to incorporate carbon capture and storage:
  1. American Clean Coal Fuels, in their Illinois Clean Fuels (ICF) project, is developing a 30,000-barrel (4,800 m3) per day biomass and coal to liquids project in Oakland, Illinois, which will market the CO
    2
    created at the plant for enhanced oil recovery applications. By combining sequestration and biomass feedstocks, the ICF project will achieve dramatic reductions in the life-cycle carbon footprint of the fuels they produce. If sufficient biomass is used, the plant should have the capability to go life-cycle carbon negative, meaning that effectively, for each gallon of their fuel that is used, carbon is pulled out of the air, and put into the ground.[96]
  2. Baard Energy, in their Ohio River Clean Fuels project, is developing a 53,000 bbl/d (8,400 m3/d) coal and biomass to liquids project, which has announced plans to market the plant's CO
    2
    for enhanced oil recovery.[97]
  3. Rentech is developing a 29,600-barrel (4,710 m3) per day coal and biomass to liquids plant in Natchez, Mississippi, which will market the plant's CO
    2
    for enhanced oil recovery. The first phase of the project is expected in 2011.[98]
  4. DKRW[who?] is developing a 15,000–20,000-barrel (2,400–3,200 m3) per day coal to liquids plant in Medicine Bow, Wyoming, which will market its plant's CO
    2
    for enhanced oil recovery. The project is expected to begin operation in 2013.[99]
In October 2009, the U.S. Department of Energy awarded grants to twelve Industrial Carbon Capture and Storage (ICCS) projects to conduct a Phase 1 feasibility study.[100] The DOE plans to select 3 to 4 of those projects to proceed into Phase 2, design and construction, with operational startup to occur by 2015. Battelle Memorial Institute, Pacific Northwest Division, Boise, Inc., and Fluor Corporation are studying a CCS system for capture and storage of CO
2
emissions associated with the pulp and paper production industry. The site of the study is the Boise White Paper L.L.C. paper mill located near the township of Wallula in Southeastern Washington State. The plant generates approximately 1.2 MMT of CO
2
annually from a set of three recovery boilers that are mainly fired with black liquor, a recycled byproduct formed during the pulping of wood for paper-making. Fluor Corporation will design a customized version of their Econamine Plus carbon capture technology. The Fluor system also will be designed to remove residual quantities of remnant air pollutants from stack gases as part of the CO
2
capture process. Battelle is leading preparation of an Environmental Information Volume (EIV) for the entire project, including geologic storage of the captured CO
2
in deep flood basalt formations that exist in the greater region. The EIV will describe the necessary site characterization work, sequestration system infrastructure, and monitoring program to support permanent sequestration of the CO
2
captured at the plant.

In addition to individual carbon capture and sequestration projects, there are a number of U.S. programs designed to research, develop, and deploy CCS technologies on a broad scale. These include the National Energy Technology Laboratory's (NETL) Carbon Sequestration Program, regional carbon sequestration partnerships and the Carbon Sequestration Leadership Forum (CSLF).[101][102]

United Kingdom

The government of the United Kingdom has launched a tender process for a CCS demonstration project. The project will use post-combustion technology on coal-fired power generation at 300–400 megawatts or equivalent. The project aims to be operational by 2014.[103][104] The Government announced in June 2008 that four companies had prequalified for the following stages of the competition: BP Alternative Energy International Limited, EON UK Plc, Peel Power Limited and Scottish Power Generation Limited.[105] BP has subsequently withdrawn from the competition, claiming it could not find a power generator partner, and RWE npower is seeking a judicial review of the process after it did not qualify.[106]

Doosan Babcock has modified their Clean Combustion Test Facility (CCTF) in Renfrew, Scotland to create the largest Oxyfuel test facility currently in the world.[citation needed] Oxyfuel firing on pulverized coal with recycled flue gas demonstrates the operation of a full scale 40 MW burner for use in coal-fired boilers. Sponsors of the project include the UK Department for Business Enterprise and Regulatory Reform (BERR,) as well as a group of industrial sponsors and university partners comprising Scottish and Southern Energy (Prime Sponsor), E.ON UK PLC, Drax Power Limited, ScottishPower, EDF Energy, Dong Energy Generation, Air Products Plc (Sponsors), and Imperial College and University of Nottingham (University Partners).[107]

In August 2010, clean energy new-comers B9 Coal announced their intention to join the competition with a CCS project in the North East of England. The proposal combines alkaline fuel cells with underground coal gasification for upwards of 90% carbon capture as a by-product. It is the only project of its kind to join the competition, using coal reserves in an environmentally friendly and efficient way.[citation needed] After costs increased to 13 billion pounds in 2011, the UK withdrew its support and ScottishPower cancelled its CCS project with Aker Clean Carbon.[citation needed]

In 2009 UK firm 2Co Energy was awarded planning permission for a £5bn power station and carbon-capture-and-storage project at Hatfield, near Doncaster and £164m of EU funding. Technology giant Samsung has agreed to take a 15% stake in the project.[108] It is planned to construct a 60 km (37 mi) pipeline from Stainforth, near Hatfield in South Yorkshire to Barmston in the East Riding of Yorkshire. CO
2
will then be stored in natural porous rock beneath the North Sea. National Grid believes the project has the potential to reduce CO
2
emissions from power stations across Yorkshire and the Humber by up to 90% with both the White Rose CCS project at Drax Power Station in North Yorkshire along with the proposed Don Valley Power Project at Hatfield benefiting from the scheme.[109][110][111]

In the Northeast of England, The Northeast of England Process Industry Cluster (NEPIC)of commodity chemical manufacturers are amongst the largest single point producers of carbon dioxide in the United Kingdom and they have created within NEPIC the Process Industry Carbon Capture and Storage Initiative[112] (PICCSI) to study the possibility of a carbon capture and storage (CCS) solution being provided for the chemical and steel manufacturing industry on Teesside, as well as for any carbon based energy production. This CCS technology option is being considered as a result of climate change regulations and the carbon taxation that could become a prohibitive cost for such energy intensive industries.

China

In Beijing, as of 2009, one major power plant is capturing and re-selling a small fraction of its CO
2
emissions.[113]

Germany

The German industrial area of Schwarze Pumpe, about 4 kilometres (2.5 mi) south of the city of Spremberg, is home to the world's first CCS coal plant.[114] The mini pilot plant is run by an Alstom-built oxy-fuel boiler and is also equipped with a flue gas cleaning facility to remove fly ash and sulphur dioxide. The Swedish company Vattenfall AB invested some 70 million Euros in the two-year project, which began operation September 9, 2008. The power plant, which is rated at 30 megawatts, is a pilot project to serve as a prototype for future full-scale power plants.[115][116] 240 tonnes a day of CO
2
are being trucked 350 kilometers (220 mi) where it will be injected into an empty gas field. Germany's BUND group called it a "fig leaf". For each tonne of coal burned, 3.6 tonnes of carbon dioxide is produced.[117] The CCS program at Schwarze Pump ended in 2014 due to unvialbe costs and energy use.[118]

German utility RWE operates a pilot-scale CO
2
scrubber at the lignite-fired Niederaußem power station built in cooperation with BASF (supplier of detergent) and Linde engineering.[119]

In Jänschwalde, Germany,[120] a plan is in the works for an Oxyfuel boiler, rated at 650 thermal MW (around 250 electric MW), which is about 20 times more than Vattenfall's 30 MW pilot plant under construction, and compares to today's largest Oxyfuel test rigs of 0.5 MW. Post-combustion capture technology will also be demonstrated at Jänschwalde.[121]

Australia

The Federal Resources and Energy Minister Martin Ferguson opened the first geosequestration project in the southern hemisphere in April 2008. The demonstration plant is near Nirranda South in South Western Victoria. (
 WikiMiniAtlas
35°19′S 149°08′E / 35.31°S 149.14°E / -35.31; 149.14) The plant is owned by the Cooperative Research Centre for Greenhouse Gas Technologies (CO2CRC). CO2CRC is a non profit research collaboration supported by government and industry. The project has stored and monitored over 65,000 tonnes of carbon dioxide-rich gas which was extracted from a natural gas reservoir via a well, compressed and piped 2.25 km to a new well. There the gas has been injected into a depleted natural gas reservoir approximately two kilometers below the surface.[122][123] The project has moved to a second stage and is investigating carbon dioxide trapping in a saline aquifer 1500 meters below the surface. The Otway Project is a research and demonstration project, focused on comprehensive monitoring and verification.[124]

This plant does not propose to capture CO
2
from coal-fired power generation, though two CO2CRC demonstration projects at a Victorian power station and research gasifier are demonstrating solvent, membrane, and adsorbent capture technologies from coal combustion.[125] Currently, only small-scale projects are storing CO
2
stripped from the products of combustion of coal burnt for electricity generation at coal-fired power stations.[126] Work currently being carried out by the GreenMag Group and the University of Newcastle and funded by the New South Wales and Australian Governments and industry intends to have a working mineral carbonation pilot plant in operation by 2013.[34]

View the full list of Zero Emission Projects for fossil fuel power plant in Europe.[127]

Limitations of CCS for power stations

Critics say large-scale CCS deployment is unproven and decades away from being commercialized. They say that it is risky and expensive and that a better option is renewable energy. Some environmental groups point out that CCS technology leaves behind dangerous waste material that has to be stored, just like nuclear power stations.[128]

Another limitation of CCS is its energy penalty. The technology is expected to use between 10 and 40 percent of the energy produced by a power station.[129] Wide-scale adoption of CCS may erase efficiency gains in coal power plants of the last 50 years, and increase resource consumption by one third. Even taking the fuel penalty into account, however, overall levels of CO
2
abatement would remain high at approximately 80–90%, compared to a plant without CCS.[130] It is possible for CCS, when combined with biomass, to result in net negative emissions.[131] Though, all of the currently (as of Feb 2011) operational BECCS (Bio-energy with carbon capture and storage) plants operate on point emissions other than power stations, such as biofuel refineries.[132]

The use of CCS can reduce CO
2
emissions from the stacks of coal power plants by 85–90% or more, but it has no effect on CO
2
emissions due to the mining and transport of coal. It will actually "increase such emissions and of air pollutants per unit of net delivered power and will increase all ecological, land-use, air-pollution, and water-pollution impacts from coal mining, transport, and processing, because the CCS system requires 25% more energy, thus 25% more coal combustion, than does a system without CCS".[133]

Another concern regards the permanence of storage schemes. Opponents to CCS claim that safe and permanent storage of CO
2
cannot be guaranteed and that even very low leakage rates could undermine any climate mitigation effect.[129] In 1986 a large leakage of naturally sequestered CO
2
rose from Lake Nyos in Cameroon and asphyxiated 1,700 people. While the carbon had been sequestered naturally, some point to the event as evidence for the potentially catastrophic effects of sequestering carbon artificially.[49][128]

On one hand, Greenpeace claims that CCS could lead to a doubling of coal plant costs.[129] It is also claimed by opponents to CCS that money spent on CCS will divert investments away from other solutions to climate change. On the other hand, CCS is pointed out as economically attractive in comparison to other forms of low carbon electricity generation and seen by the IPCC and others as a critical component for meeting mitigation targets such as 450 ppm and 350 ppm.[134][135][136]

Cost

Although the processes involved in CCS have been demonstrated in other industrial applications, no commercial scale projects which integrate these processes exist; the costs therefore are somewhat uncertain. Some recent credible estimates indicate that the cost of capturing and storing carbon dioxide is US$60 per ton,[137] corresponding to an increase in electricity prices of about US 6c per kWh (based on typical coal-fired power plant emissions of 2.13 pounds CO
2
per kWh). This would double the typical US industrial electricity price (now at around 6c per kWh) and increase the typical retail residential electricity price by about 50% (assuming 100% of power is from coal, which may not necessarily be the case, as this varies from state to state). Similar (approximate) price increases would likely be expected in coal dependent countries such as Australia, because the capture technology and chemistry, as well as the transport and injection costs from such power plants would not, in an overall sense, vary significantly from country to country.[citation needed]

The reasons that CCS is expected to cause such power price increases are several. Firstly, the increased energy requirements of capturing and compressing CO
2
significantly raises the operating costs of CCS-equipped power plants. In addition, there are added investment and capital costs. The process would increase the fuel requirement of a plant with CCS by about 25% for a coal-fired plant, and about 15% for a gas-fired plant.[4] The cost of this extra fuel, as well as storage and other system costs, are estimated to increase the costs of energy from a power plant with CCS by 30–60%, depending on the specific circumstances. Pre-commercial CCS demonstration projects are likely to be more expensive than mature CCS technology; the total additional costs of an early large-scale CCS demonstration project are estimated to be €0.5-1.1 billion per project over the project lifetime. Other applications are possible. In the belief that use of sequestered carbon could be harnessed to offset the cost of capture and storage, Walker Architects published the first CO
2
gas CAES application, proposing the use of sequestered CO
2
for Energy Storage on October 24, 2008. To date the feasibility of such potential offsets to the cost have not been examined.[138]

An estimate of costs of energy with and without CCS (2002 US$ per kWh)[4]
Natural gas combined cycle Pulverized coal Integrated gasification combined cycle
Without capture (reference plant) 0.03–0.05 0.04–0.05 0.04–0.06
With capture and geological storage 0.04–0.08 0.06–0.10 0.06–0.09
(Cost of capture and geological storage) 0.01–0.03 0.02–0.05 0.02–0.03
With capture and Enhanced oil recovery 0.04–0.07 0.05–0.08 0.04–0.08

All costs refer to costs for energy from newly built, large-scale plants. Natural gas combined cycle costs are based on natural gas prices of US$2.80–4.40 per GJ (LHV based). Energy costs for PC and IGCC are based on bituminous coal costs of US$1.00–1.50 per GJ LHV. Note that the costs are very dependent on fuel prices (which change continuously), in addition to other factors such as capital costs. Also note that for EOR, the savings are greater for higher oil prices. Current gas and oil prices are substantially higher than the figures used here. All figures in the table are from Table 8.3a in [IPCC, 2005].[4]

The cost of CCS depends on the cost of capture and storage, which varies according to the method used. Geological storage in saline formations or depleted oil or gas fields typically cost US$0.50–8.00 per tonne of CO
2
injected, plus an additional US$0.10–0.30 for monitoring costs. When storage is combined with enhanced oil recovery to extract extra oil from an oil field, however, the storage could yield net benefits of US$10–16 per tonne of CO
2
injected (based on 2003 oil prices). This would likely negate some of the effect of the carbon capture when the oil was burnt as fuel. Even taking this into account, as the table above shows, the benefits do not outweigh the extra costs of capture.[citation needed]

Cost of electricity generated by different sources including those incorporating CCS technologies can be found in cost of electricity by source. If CO
2
capture was part of a fuel cycle then the CO
2
would have value rather than be a cost. The proposed Solar Fuel or methane cycle proposed by the Fraunhofer Society[citation needed] amongst others is an example. This "solar fuel"[139] cycle uses the excess electrical renewable energy to create hydrogen via electrolysis of water.[140][141] The hydrogen is then combined with CO
2
to create synthetic natural gas SNG and stored in the gas network. See the latest Cost Report on the Cost of CO
2
Capture produced by the Zero Emissions Platform

Governments around the world have provided a range of different types of funding support to CCS demonstration projects, including tax credits, allocations and grants. The funding is associated with both a desire to accelerate innovation activities for CCS as a low-carbon technology and the need for economic stimulus activities. As of 2011, approximately US$23.5bn has been made available to support large-scale CCS demonstration projects around the world.[142]

Carbon Capture and Storage and the Kyoto Protocol

One way to finance future CCS projects could be through the Clean Development Mechanism of the Kyoto Protocol. At COP16 in 2010, The Subsidiary Body for Scientific and Technological Advice, at its thirty-third session, issued a draft document recommending the inclusion of Carbon dioxide capture and storage in geological formations in Clean Development Mechanism project activities.[143] At COP17 in Durban, a final agreement was reached enabling CCS projects to receive support through the Clean Development Mechanism.[144]

Environmental effects

The theoretical merit of CCS systems is the reduction of CO
2
emissions by up to 90%, depending on plant type. Generally, environmental effects from use of CCS arise during power production, CO
2
capture, transport, and storage. Issues relating to storage are discussed in those sections.

Additional energy is required for CO
2
capture, and this means that substantially more fuel has to be used to produce the same amount of power, depending on the plant type. For new super-critical pulverized coal (PC) plants using current technology, the extra energy requirements range from 24 to 40%, while for natural gas combined cycle (NGCC) plants the range is 11–22% and for coal-based gasification combined cycle (IGCC) systems it is 14–25% [IPCC, 2005].[145] Obviously, fuel use and environmental problems arising from mining and extraction of coal or gas increase accordingly. Plants equipped with flue-gas desulfurization (FGD) systems for sulfur dioxide control require proportionally greater amounts of limestone, and systems equipped with selective catalytic reduction systems for nitrogen oxides produced during combustion require proportionally greater amounts of ammonia.

IPCC has provided estimates of air emissions from various CCS plant designs (see table below). While CO
2
is drastically reduced though never completely captured, emissions of air pollutants increase significantly, generally due to the energy penalty of capture. Hence, the use of CCS entails a reduction in air quality. Type and amount of air pollutants still depends on technology. CO
2
is captured with alkaline solvents catching the acidic CO
2
at low temperatures in the absorber and releasing CO
2
at higher temperatures in a desorber. Chilled Ammonia CCS Plants have inevitable ammonia emissions to air. "Functionalized Ammonia" emit less ammonia, but amines may form secondary amines and these will emit volatile nitrosamines[146] by a side reaction with nitrogendioxide, which is present in any flue gas even after DeNOx. Nevertheless, there are advanced amines in testing with little to no vapor pressure to avoid these amine- and consecutive nitrosamine emissions. Nevertheless, all the capture plants amines have in common, that practically 100% of remaining sulfur dioxide from the plant is washed out of the flue gas, the same applies to dust/ash.

Emissions to air from plants with CCS (kg/(MW•h))
Natural gas combined cycle Pulverized coal Integrated gasification combined cycle
CO
2
43 (-89%) 107 (−87%) 97 (−88%)
NOX 0.11 (+22%) 0.77 (+31%) 0.1 (+11%)
SOX - 0.001 (−99.7%) 0.33 (+17.9%)
Ammonia 0.002 (before: 0) 0.23 (+2200%) -

Based on Table 3.5 in [IPCC, 2005]. Between brackets the increase or decrease compared to a similar plant without CCS.

Artificial photosynthesis



From Wikipedia, the free encyclopedia


A sample of a photoelectric cell in a lab environment. Catalysts are added to the cell, which is submerged in water and illuminated by simulated sunlight. The bubbles seen are oxygen (forming on the front of the cell) and hydrogen (forming on the back of the cell).

Artificial photosynthesis is a chemical process that replicates the natural process of photosynthesis, a process that converts sunlight, water, and carbon dioxide into carbohydrates and oxygen. The term is commonly used to refer to any scheme for capturing and storing the energy from sunlight in the chemical bonds of a fuel (a solar fuel). Photocatalytic water splitting converts water into Hydrogen Ions and oxygen, and is a main research area in artificial photosynthesis. Light-driven carbon dioxide reduction is another studied process, replicating natural carbon fixation.

Research developed in this field encompasses design and assembly of devices (and their components) for the direct production of solar fuels, photoelectrochemistry and its application in fuel cells, and engineering of enzymes and photoautotrophic microorganisms for microbial biofuel and biohydrogen production from sunlight. Many, if not most, of the artificial approaches are bio-inspired, i.e., they rely on biomimetics.

Overview

The photosynthetic reaction can be divided into two half-reactions (oxidation and reduction), both of which are essential to producing fuel. In plant photosynthesis, water molecules are photo-oxidized to release oxygen and protons. The second stage of plant photosynthesis (also known as the Calvin-Benson cycle) is a light-independent reaction that converts carbon dioxide into glucose. Researchers of artificial photosynthesis are developing photocatalysts to perform both of these reactions separately. Furthermore, the protons resulting from water splitting can be used for hydrogen production. These catalysts must be able to react quickly and absorb a large percentage of solar photons.[1]

Whereas photovoltaics can provide direct electrical current from sunlight, the inefficiency of fuel production from photovoltaic electricity (indirect process) and the fact sunshine is not constant throughout time sets a limit to its use.[2][3] A way of using natural photosynthesis is via the production of biofuel through biomass, also an indirect process that suffers from low energy conversion efficiency (due to photosynthesis' own low efficiency in converting sunlight to biomass), and clashes with the increasing need of land mass for human food production.[4] Artificial photosynthesis aims then to produce a fuel from sunlight that can be stored and used when sunlight is not available, by using direct processes, that is, to produce a solar fuel. With the development of catalysts able to reproduce the key steps of photosynthesis, water and sunlight would ultimately be the only needed sources for clean energy production. The only by-product would be oxygen, and production of a solar fuel has the potential to be cheaper than gasoline.[5]

One process for the creation of a clean and affordable energy supply is the development of photocatalytic water splitting under solar light. This method of sustainable hydrogen production is a key objective in the development of alternative energy systems of the future.[6] It is also predicted to be one of the more, if not the most, efficient ways of obtaining hydrogen from water.[7] The conversion of solar energy into hydrogen via a water-splitting process assisted by photosemiconductor catalysts is one of the most promising technologies in development.[citation needed] This process has the potential for large quantities of hydrogen to be generated in an ecologically sound method.[citation needed] The conversion of solar energy into a clean fuel (H2) under ambient conditions is one of the greatest challenges facing scientists in the twenty-first century.[8]

Two approaches are generally recognized in the construction of solar fuel cells for hydrogen production:[9]
  • A homogeneous system is one where catalysts are not compartmentalized, that is, components are present in the same compartment. This means that hydrogen and oxygen are produced in the same location. This can be a drawback, since they compose an explosive mixture, demanding further gas purification. Also, all components must be active in approximately the same conditions (e.g., pH).
  • A heterogeneous system has two separate electrodes, an anode and a cathode, making possible the separation of oxygen and hydrogen production. Furthermore, different components do not necessarily need to work in the same conditions. However, the increased complexity of these systems makes them harder to develop and more expensive.
Another area of research within artificial photosynthesis is the selection and manipulation of photosynthetic microorganisms, namely green microalgae and cyanobacteria, for the production of solar fuels. Many strains are able to produce hydrogen naturally, and scientists are working to improve them.[10] Algae biofuels such as butanol and methanol are produced both at laboratory and commercial scales. This approach has benefited with the development of synthetic biology,[10] which is also being explored by the J. Craig Venter Institute to produce a synthetic organism capable of biofuel production.[11][12]

History

In the late 60s, Akira Fujishima discovered the photocatalytic properties of titanium dioxide, the so-called Honda-Fujishima effect, which could be used for hydrolysis.[13]

The Swedish Consortium for Artificial Photosynthesis, the first of its kind, was established in 1994 as a collaboration between groups of three different universities, Lund, Uppsala and Stockholm, being presently active around Lund and the Ångström Laboratories in Uppsala.[14] The consortium was built with a multidisciplinary approach to focus on learning from natural photosynthesis and applying this knowledge in biomimetic systems.[15]

Research in artificial photosynthesis is undergoing a boom at the beginning of the 21st century.[2] In 2000, Commonwealth Scientific and Industrial Research Organisation (CSIRO) researchers publicize their intent to focus on carbon dioxide capture and conversion to hydrocarbons.[16][17] In 2003, the Brookhaven National Laboratory announced the discovery of an important intermediate step in the reduction of CO2 to CO (the simplest possible carbon dioxide reduction reaction), which could lead to better catalyst designing.[18][19]

One of the drawbacks of artificial systems for water-splitting catalysts is their general reliance on scarce, expensive elements, such as ruthenium or rhenium.[2] With the funding of the United States Air Force Office of Scientific Research,[20] in 2008, MIT chemist and head of the Solar Revolution Project Daniel G. Nocera and postdoctoral fellow Matthew Kanan attempted to circumvent this issue by using a catalyst containing the cheaper and more abundant elements cobalt and phosphate.[21][22] The catalyst was able to split water into oxygen and protons using sunlight, and could potentially be coupled to a hydrogen-producing catalyst such as platinum. Furthermore, while the catalyst broke down during catalysis, it could self-repair.[23] This experimental catalyst design was considered a major breakthrough in the field by many researchers.[24][25]

Whereas CO is the prime reduction product of CO2, more complex carbon compounds are usually desired. In 2008, Princeton chemistry professor Andrew B. Bocarsly reported the direct conversion of carbon dioxide and water to methanol using solar energy in a highly efficient photochemical cell.[26]

While Nocera and coworkers had accomplished water splitting to oxygen and protons, a light-driven process to produce hydrogen from protons still needed to be developed. In 2009, the Leibniz Institute for Catalysis reported inexpensive iron carbonyl complexes able to do just this.[27][28] In the same year, researchers at the University of East Anglia also used iron carbonyl compounds to achieve photoelectrochemical hydrogen production with 60% efficiency, this time using a gold electrode covered with layers of indium phosphide to which the iron complexes were linked.[29] Both these processes used a molecular approach, where discrete nanoparticles are responsible for catalysis.

Visible light water splitting with a one piece multijunction cell was first demonstrated and patented by William Ayers at Energy Conversion Devices in 1983.[30] This group demonstrated water photolysis into hydrogen and oxygen, now referred to as an "artificial leaf" or "wireless solar water splitting" with a low cost, thin film amorphous silicon multijunction cell directly immersed in water. Hydrogen evolved on the front amorphous silicon surface decorated with various catalysts while oxygen evolved off the back metal substrate which also eliminated the problem of mixed hydrogen/oxygen gas evolution. A Nafion membrane above the immersed cell provided a path for proton transport. The higher photovoltage available from the multijuction thin film cell with visible light was a major advance over previous photolysis attempts with UV sensitive single junction cells. The group's patent also lists several other semiconductor multijunction compositions in addition to amorphous silicon.

In 2009, F. del Valle and K. Domen showed the impact of the thermal treatment in a closed atmosphere using Cd1-xZnxS photocatalysts. Cd1-xZnxS solid solution reports high activity in hydrogen production from water splitting under sunlight irradiation.[31] A mixed heterogeneous/molecular approach by researchers at the University of California, Santa Cruz, in 2010, using both nitrogen-doped and cadmium selenide quantum dots-sensitized titanium dioxide nanoparticles and nanowires, also yielded photoproduced hydrogen.[32]

Artificial photosynthesis remained an academic field for many years. However, in the beginning of 2009, Mitsubishi Chemical Holdings was reported to be developing its own artificial photosynthesis research by using sunlight, water and carbon dioxide to "create the carbon building blocks from which resins, plastics and fibers can be synthesized."[33] This was confirmed with the establishment of the KAITEKI Institute later that year, with carbon dioxide reduction through artificial photosynthesis as one of the main goals.[34][35]

In 2010, the DOE established, as one of its Energy Innovation Hubs, the Joint Center for Artificial Photosynthesis.[36] The mission of JCAP is to find a cost-effective method to produce fuels using only sunlight, water, and carbon-dioxide as inputs.  JCAP is led by a team from Caltech, led by Professor Nathan Lewis and brings together more than 120 scientists and engineers from Caltech and its lead partner, Lawrence Berkeley National Laboratory. JCAP also draws on the expertise and capabilities of key partners from Stanford University, the University of California at Berkeley, UCSB, UCI, and UCSD, and the Stanford Linear Accelerator.  In addition, JCAP serves as a central hub for other solar fuels research teams across the United States, including 20 DOE Energy Frontier Research Center.  The program has a budget of $122M over five years, subject to Congressional appropriation[37]

Also in 2010, a team led by professor David Wendell at the University of Cincinnati successfully demonstrated photosynthesis in an artificial construct consisting of enzymes suspended in frog foam.[38]

In 2011, Daniel Nocera and his research team announced the creation of the first practical artificial leaf. In a speech at the 241st National Meeting of the American Chemical Society, Nocera described an advanced solar cell the size of a poker card capable of splitting water into oxygen and hydrogen, approximately ten times more efficient than natural photosynthesis.[39] The cell is mostly made of inexpensive materials that are widely available, works under simple conditions, and shows increased stability over previous catalysts: in laboratory studies, the authors demonstrated that an artificial leaf prototype could operate continuously for at least forty-five hours without a drop in activity.[40] In May 2012, Sun Catalytix, the startup based on Nocera's research, stated that it will not be scaling up the prototype as the device offers few savings over other ways to make hydrogen from sunlight.[41] Leading experts in the field have supported a proposal for a Global Project on Artificial Photosynthesis as a combined energy security and climate change solution.[42]

Current research

In energy terms, natural photosynthesis can be divided in three steps:[9][15]

A triad assembly, with a photosensitizer (P) linked in tandem to a water oxidation catalyst (D) and a hydrogen evolving catalyst (A). Electrons flow from D to A when catalysis occurs.

Using biomimetic approaches, artificial photosynthesis tries to construct systems doing the same type of processes. Ideally, a triad assembly could oxidize water with one catalyst, reduce protons with another and have a photosensitizer molecule to power the whole system. One of the simplest designs is where the photosensitizer is linked in tandem between a water oxidation catalyst and a hydrogen evolving catalyst:
  • The photosensitizer transfers electrons to the hydrogen catalyst when hit by light, becoming oxidized in the process.
  • This drives the water splitting catalyst to donate electrons to the photosensitizer. In a triad assembly, such a catalyst is often referred to as a donor. The oxidized donor is able to perform water oxidation.
The state of the triad with one catalyst oxidized on one end and the second one reduced on the other end of the triad is referred to as a charge separation, and is a driving force for further electron transfer, and consequently catalysis, to occur. The different components may be assembled in diverse ways, such as supramolecular complexes, compartmentalized cells, or linearly, covalently linked molecules.[9]

Research into finding catalysts that can convert water, carbon dioxide, and sunlight to carbohydrates or hydrogen is a current, active field. By studying the natural oxygen-evolving complex, researchers have developed catalysts such as the "blue dimer" to mimic its function. Photoelectrochemical cells that reduce carbon dioxide into carbon monoxide (CO), formic acid (HCOOH) and methanol (CH3OH) are under development.[43] However, these catalysts are still very inefficient.[5]

Hydrogen catalysts

Hydrogen is the simplest solar fuel to synthesize, since it involves only the transference of two electrons to two protons. It must, however, be done stepwise, with formation of an intermediate hydride anion:
2 e + 2 H+ ↔ H+ + H ↔ H2
The proton-to-hydrogen converting catalysts present in nature are hydrogenases. These are enzymes that can either reduce protons to molecular hydrogen or oxidize hydrogen to protons and electrons. Spectroscopic and crystallographic studies spanning several decades have resulted in a good understanding of both the structure and mechanism of hydrogenase catalysis.[44][45] Using this information, several molecules mimicking the structure of the active site of both nickel-iron and iron-iron hydrogenases have been synthesized.[9][46] Other catalysts are not structural mimics of hydrogenase but rather functional ones. Synthesized catalysts include structural H-cluster models,[9][47] a dirhodium photocatalyst,[48] and cobalt catalysts.[9][49]

Water-oxidizing catalysts

Water oxidation is a more complex chemical reaction than proton reduction. In nature, the oxygen-evolving complex performs this reaction by accumulating reducing equivalents (electrons) in a manganese-calcium cluster within photosystem II (PS II), then delivering them to water molecules, with the resulting production of molecular oxygen and protons:
2 H2O → O2 + 4 H+ + 4e
Without a catalyst (natural or artificial), this reaction is very endothermic, requiring high temperatures (at least 2500 K).[7]

The exact structure of the oxygen-evolving complex has been hard to determine experimentally.[50] As of 2011, the most detailed model was from a 1.9 Å resolution crystal structure of photosystem II.[51] The complex is a cluster containing four manganese and one calcium ions, but the exact location and mechanism of water oxidation within the cluster is unknown. Nevertheless, bio-inspired manganese and manganese-calcium complexes have been synthesized, such as [Mn4O4] cubanes, some with catalytic activity.[52]

Some ruthenium complexes, such as the dinuclear µ-oxo-bridged "blue dimer" (the first of its kind to be synthesized), are capable of light-driven water oxidation, thanks to being able to form high valence states.[9] In this case, the ruthenium complex acts as both photosensitizer and catalyst.

Many metal oxides have been found to have water oxidation catalytic activity, including ruthenium(IV) oxide (RuO2), iridium(IV) oxide (IrO2), cobalt oxides (including nickel-doped Co3O4), manganese oxide (including MnO2(birnessite),Mn2O3), and a mix of Mn2O3 with CaMn2O4. Oxides are easier to obtain than molecular catalysts, especially those from relatively abundant transition metals (cobalt and manganese), but suffer from low turnover frequency and slow electron transfer properties, and their mechanism of action is hard to decipher and, therefore, to adjust.[6]

Recently Metal-Organic Framework (MOF)-based materials have been shown to be a highly promising candidate for water oxidation with first row transition metals.[53][54] The stability and tunability of this system is projected to be highly beneficial for future development.[55]

Photosensitizers


Structure of [Ru(bipy)3]2+, a broadly used photosensitizer.

Nature uses pigments, mainly chlorophylls, to absorb a broad part of the visible spectrum. Artificial systems can use either one type of pigment with a broad absorption range or combine several pigments for the same purpose.

Ruthenium polypyridine complexes, in particular tris(bipyridine)ruthenium(II) and its derivatives, have been extensively used in hydrogen photoproduction due to their efficient visible light absorption and long-lived consequent metal-to-ligand charge transfer excited state, which makes the complexes strong reducing agents.[9] Other noble metal-containing complexes used include ones with platinum, rhodium and iridium.[9]

Metal-free organic complexes have also been successfully employed as photosensitizers. Examples include eosin Y and rose bengal.[9] Pyrrole rings such as porphyrins have also been used in coating nanomaterials or semiconductors for both homogeneous and heterogeneous catalysis.[6][43]

Carbon dioxide reduction catalysts

In nature, carbon fixation is done by green plants using the enzyme RuBisCO as a part of the Calvin cycle. RuBisCO is a rather slow catalyst compared to the vast majority of other enzymes,
incorporating only a few molecules of carbon dioxide into ribulose-1,5-bisphosphate per minute, but does so at atmospheric pressure and in mild, biological conditions.[56] The resulting product is further reduced and eventually used in the synthesis of glucose, which in turn is a precursor to more complex carbohydrates, such as cellulose and starch. The process consumes energy in the form of ATP and NADPH.

Artificial CO2 reduction for fuel production aims mostly at producing reduced carbon compounds from atmospheric CO2. Some transition metal polyphosphine complexes have been developed for this end; however, they usually require previous concentration of CO2 before use, and carriers (molecules that would fixate CO2) that are both stable in aerobic conditions and able to concentrate CO2 at atmospheric concentrations haven't been yet developed.[57] The simplest product from CO2 reduction is carbon monoxide (CO), but for fuel development, further reduction is needed, and a key step also needing further development is the transfer of hydride anions to CO.[57]

Other materials and components

Charge separation is a key property of dyad and triad assemblies. Some nanomaterials employed are fullerenes (such as carbon nanotubes), a strategy that explores the pi-bonding properties of these materials.[6] Diverse modifications (covalent and non-covalent) of carbon nanotubes have been attempted to increase the efficiency of charge separation, including the addition of ferrocene and pyrrole-like molecules such as porphyrins and phthalocyanines.[6]

Since photodamage is usually a consequence in many of the tested systems after a period of exposure to light, bio-inspired photoprotectants have been tested, such as carotenoids (which are used in photosynthesis as natural protectants).[58]

Light-driven methodologies under development

Photoelectrochemical cells

Photoelectrochemical cells are a heterogeneous system that use light to produce either electricity or hydrogen. The vast majority of photoelectrochemical cells use semiconductors as catalysts.[43] There have been attempts to use synthetic manganese complex-impregnated Nafion as a working electrode, but it has been since shown that the catalytically active species is actually the broken-down complex.[59]
A promising, emerging type of solar cell is the dye-sensitized solar cell. This type of cell still depends on a semiconductor (such as TiO2) for current conduction on one electrode, but with a coating of an organic or inorganic dye that acts as a photosensitizer; the counter electrode is a platinum catalyst for H2 production.[43] These cells have a self-repair mechanism and solar-to-electricity conversion efficiencies rivaling those of solid-state semiconductor ones.[43]

Photocatalytic water splitting in homogeneous systems

Direct water oxidation by photocatalysts is a more efficient usage of solar energy than photoelectrochemical water splitting because it avoids an intermediate thermal or electrical energy conversion step.[60]
Bio-inspired manganese clusters have been shown to possess water oxidation activity when adsorbed on clays together with ruthenium photosensitizers, although with low turnover numbers.[9]

As mentioned above, some ruthenium complexes are able to oxidize water under solar light irradiation.[9] Although their photostability is still an issue, many can be reactivated by a simple adjustment of the conditions they work in.[9] Improvement of catalyst stability has been tried resorting to polyoxometalates, in particular ruthenium-based ones.[6][9]

Whereas a fully functional artificial system is usually envisioned when constructing a water splitting device, some mixed approaches have been tried. One of these involve the use of a gold electrode to which photosystem II is linked; an electrical current is detected upon illumination.[61]

Hydrogen-producing artificial systems


A H-cluster FeFe hydrogenase model compound covalently linked to a ruthenium photosensitizer. The ruthenium complex absorbs light and transduces its energy to the iron compound, which can then reduce protons to H2.

The simplest photocatalytic hydrogen production unit consists of a hydrogen-evolving catalyst linked to a photosensitizer.[62] In this dyad[disambiguation needed] assembly, a so-called sacrificial donor for the photosensitizer is needed, that is, one that is externally supplied and replenished; the photosensitizer donates the necessary reducing equivalents to the hydrogen-evolving catalyst, which uses protons from a solution where it is immersed or dissolved in. Cobalt compounds such as cobaloximes are some of the best hydrogen catalysts, having been coupled to both metal-containing and metal-free photosensitizers.[9][63] The first H-cluster models linked to photosensitizers (mostly ruthenium photosensitizers, but also porphyrin-derived ones) were prepared in the early 2000s.[9] Both types of assembly are under development to improve their stability and increase their turnover numbers, both necessary for constructing a sturdy, long-lived solar fuel cell.

As with water oxidation catalysis, not only fully artificial systems have been idealized: hydrogenase enzymes themselves have been engineered for photoproduction of hydrogen, by coupling the enzyme to an artificial photosensitizer, such as [Ru(bipy)3]2+ or even photosystem I.[9][62]

NADP+/NADPH coenzyme-inspired catalyst

In natural photosynthesis, the NADP+ coenzyme is reducible to NADPH through binding of a proton and two electrons. This reduced form can then deliver the proton and electrons, potentially as a hydride, to reactions that culminate in the production of carbohydrates (the Calvin cycle). The coenzyme is recyclable in a natural photosynthetic cycle, but this process is yet to be artificially replicated.

A current goal is to obtain an NADPH-inspired catalyst capable of recreating the natural cyclic process. Utilizing light, hydride donors would be regenerated and produced where the molecules are continuously used in a closed cycle. Brookhaven chemists are now using a ruthenium-based complex to serve as the acting model. The complex is proven to perform correspondingly with NADP+/NADPH, behaving as the foundation for the proton and two electrons needed to convert acetone to isopropanol.

Currently, Brookhaven researchers are aiming to find ways for light to generate the hydride donors. The general idea is to use this process to produce fuels from carbon dioxide.[64]

Photobiological production of fuels

Some photoautotrophic microorganisms can, under certain conditions, produce hydrogen. Nitrogen-fixing microorganisms, such as filamentous cyanobacteria, possess the enzyme nitrogenase, responsible for conversion of atmospheric N2 into ammonia; molecular hydrogen is a byproduct of this reaction, and is many times not released by the microorganism, but rather taken up by a hydrogen-oxidizing (uptake) hydrogenase. One way of forcing these organisms to produce hydrogen is then to annihilate uptake hydrogenase activity. This has been done on a strain of Nostoc punctiforme: one of the structural genes of the NiFe uptake hydrogenase was inactivated by insertional mutagenesis, and the mutant strain showed hydrogen evolution under illumination.[65]

Many of these photoautotrophs also have bidirectional hydrogenases, which can produce hydrogen under certain conditions. However, other energy-demanding metabolic pathways can compete with the necessary electrons for proton reduction, decreasing the efficiency of the overall process; also, these hydrogenases are very sensitive to oxygen.[10]

Several carbon-based biofuels have also been produced using cyanobacteria, such as 1-butanol.[66]
Synthetic biology techniques are predicted to be useful in this field. Microbiological and enzymatic engineering have the potential of improving enzyme efficiency and robustness, as well as constructing new biofuel-producing metabolic pathways in photoautotrophs that previously lack them, or improving on the existing ones.[10][66] Another field under development is the optimization of photobioreactors for commercial application.[67]

Employed research techniques

Research in artificial photosynthesis is necessarily a multidisciplinary field, requiring a multitude of different expertise.[10] Some techniques employed in making and investigating catalysts and solar cells include:

Advantages, disadvantages, and efficiency

Advantages of solar fuel production through artificial photosynthesis include:
  • The solar energy can be immediately converted and stored. In photovoltaic cells, sunlight is converted into electricity and then converted again into chemical energy for storage, with some necessary loss of energy associated with the second conversion.
  • The byproducts of these reactions are environmentally friendly. Artificially photosynthesized fuel would be a carbon-neutral source of energy, which could be used for transportation or homes.
Disadvantages include:
  • Materials used for artificial photosynthesis often corrode in water, so they may be less stable than photovoltaics over long periods of time. Most hydrogen catalysts are very sensitive to oxygen, being inactivated or degraded in its presence; also, photodamage may occur over time.[9][62]
  • The overall cost is not yet advantageous enough to compete with fossil fuels as a commercially viable source of energy.[3]
A concern usually addressed in catalyst design is efficiency, in particular how much of the incident light can be used in a system in practice. This is comparable with photosynthetic efficiency, where light-to-chemical-energy conversion is measured. Photosynthetic organisms are able to collect about 50% of incident solar radiation,[68] but photochemical cells could use materials absorbing a wider range of solar radiation. It is however not straightforward to compare overall fuel production between natural and artificial systems: for example, plants have a theoretical threshold of 12% efficiency of glucose formation from photosynthesis, while a carbon reducing catalyst may go beyond this value.[68] However, plants are efficient in using CO2 at atmospheric concentrations, something that artificial catalysts still cannot perform.[69]

Algorithmic information theory

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