Carbon dioxide scrubber
A carbon dioxide scrubber is a device which absorbs carbon dioxide (CO2). It is used to treat exhaust gases from industrial plants or from exhaled air in life support systems such as rebreathers or in spacecraft, submersible craft or airtight chambers. Carbon dioxide scrubbers are also used in controlled atmosphere (CA) storage. They have also been researched for carbon capture.
The dominant application for CO2 scrubbing is for removal of CO2 from the exhaust of coal- and gas-fired power plants. Virtually the only technology being seriously evaluated involves the use of various amines, e.g. monoethanolamine. Cold solutions of these organic compounds bind CO2, but the binding is reversed at higher temperatures:
- CO2 + 2 HOCH2CH2NH2 ↔ HOCH2CH2NH3+ + HOCH2CH2NH(CO2−)
Minerals and zeolites
Several minerals and mineral-like materials reversibly bind CO2. Most often, these minerals are oxides, and often the CO2 is bound as carbonate. Carbon dioxide reacts with quicklime (calcium oxide) to form limestone (calcium carbonate), in a process called carbonate looping. Other minerals include serpentinite, a magnesium silicate hydroxide, and olivine. Molecular sieves also function in this capacity.
Various scrubbing processes have been proposed to remove CO2 from the air, or from flue gases. These usually involve using a variant of the Kraft process. Scrubbing processes may be based on sodium hydroxide. The CO2 is absorbed into solution, transferred to lime via a process called causticization and released in a kiln. With some modifications to the existing processes, mainly an oxygen-fired kiln, the end result is a concentrated stream of CO2 ready for storage or use in fuels. An alternative to this thermo-chemical process is an electrical one in which a nominal voltage is applied across the carbonate solution to release the CO2. While simpler, this electrical process consumes more energy as it splits water at the same time. Since it depends on electricity, the electricity needs to be renewable, like PV. Otherwise the CO2 produced during electricity production has to be taken into account. Early incarnations of air capture used electricity as the energy source; hence, were dependent on a carbon-free source. Thermal air capture systems use heat generated on-site, which reduces the inefficiencies associated with off-site electricity production, but of course it still needs a source of (carbon-free) heat. Concentrated solar power is an example of such a source.
Zeman and Lackner outlined a specific method of air capture.
First, CO2 is absorbed by an alkaline NaOH solution to produce dissolved sodium carbonate. The absorption reaction is a gas liquid reaction, strongly exothermic, here:
- 2NaOH(aq) + CO2(g) → Na2CO3(aq) + H2O(l)
- Na2CO3(aq) + Ca(OH)2(s) → 2NaOH(aq) + CaCO3(s)
- ΔH° = -5.3 kJ/mol
Causticization is performed ubiquitously in the pulp and paper industry and readily transfers 94% of the carbonate ions from the sodium to the calcium cation. Subsequently, the calcium carbonate precipitate is filtered from solution and thermally decomposed to produce gaseous CO2. The calcination reaction is the only endothermic reaction in the process and is shown here:
- CaCO3(s) → CaO(s) + CO2(g)
- ΔH° = + 179.2 kJ/mol
The thermal decomposition of calcite is performed in a lime kiln fired with oxygen in order to avoid an additional gas separation step. Hydration of the lime (CaO) completes the cycle. Lime hydration is an exothermic reaction that can be performed with water or steam. Using water, it is a liquid/solid reaction as shown here:
- CaO(s) + H2O(l) → Ca(OH)2(s)
- ΔH° = -64.5 kJ/mol
Other strong bases such as soda lime, sodium hydroxide, potassium hydroxide, and lithium hydroxide are able to remove carbon dioxide by chemically reacting with it. In particular, lithium hydroxide was used aboard spacecraft, such as in the Apollo program, to remove carbon dioxide from the atmosphere. It reacts with carbon dioxide to make lithium carbonate. Recently lithium hydroxide absorbent technology has been adapted for use in anesthesia machines. Anesthesia machines which provide life support and inhaled agents during surgery typically employ a closed circuit necessitating the removal of carbon dioxide exhaled by the patient. Lithium hydroxide may offer some safety and convenience benefits over the older calcium based products.
- 2 LiOH(s) + 2 H2O(g) → 2 LiOH·H2O(s)
- 2 LiOH·H2O(s) + CO2(g) → Li2CO3(s) + 3 H2O(g)
The net reaction being:
- 2LiOH(s) + CO2(g) → Li2CO3(s) + H2O(g)
Regenerative carbon dioxide removal system
The regenerative carbon dioxide removal system (RCRS) on the space shuttle orbiter used a two-bed system that provided continuous removal of carbon dioxide without expendable products. Regenerable systems allowed a shuttle mission a longer stay in space without having to replenish its sorbent canisters. Older lithium hydroxide (LiOH)-based systems, which are non-regenerable, were replaced by regenerable metal-oxide-based systems. A system based on metal oxide primarily consisted of a metal oxide sorbent canister and a regenerator assembly. It worked by removing carbon dioxide using a sorbent material and then regenerating the sorbent material. The metal-oxide sorbent canister was regenerated by pumping air at approximately 400 °F (204 °C) through it at a standard flow rate of 7.5 cu ft/min (0.0035 m3/s) for 10 hours.
Activated carbon can be used as a carbon dioxide scrubber. Air with high carbon dioxide content, such as air from fruit storage locations, can be blown through beds of activated carbon and the carbon dioxide will adsorb onto the activated carbon. Once the bed is saturated it must then be "regenerated" by blowing low carbon dioxide air, such as ambient air, through the bed. This will release the carbon dioxide from the bed, and it can then be used to scrub again, leaving the net amount of carbon dioxide in the air the same as when the process was started.
Metal-organic frameworks (MOFs)
Metal-organic frameworks are one of the most promising new technologies for carbon dioxide capture and sequestration via adsorption. Although no large-scale commercial technology exists nowadays, several research studies have indicated the great potential that MOFs have as a CO2 adsorbent. It's characteristics, such as pore structure and surface functions can be easily tuned to improve CO2 selectivity over other gases.
A MOF could be specifically designed to act like a CO2 removal agent in post-combustion power plants. In this scenario, the flue gas would pass through a bed packed with a MOF material, where CO2 would be stripped. After saturation is reached, CO2 could be desorbed by doing a pressure or temperature swing. Carbon dioxide could then be compressed to supercritical conditions in order to be stored underground or utilized in enhanced oil recovery processes. However, this is not possible in large scale yet due to several difficulties, one of those being the production of MOFs in great quantities.
Another problem is the availability of metals necessary to synthesize MOFs. In a hypothetical scenario where these materials are used to capture all CO2 needed to avoid global warming issues, such as maintaining a global temperature rise less than 2oC above the pre-industrial average temperature, we would need more metals than are available on Earth. For example, to synthesize all MOFs that using vanadium, we would need 1620% of 2010 global reserves. Even if using magnesium-based MOFs, which have demonstrated a great capacity to adsorb CO2, we would need 14% of 2010 global reserves, which is a considerable amount. Also, extensive mining would be necessary, leading to more potential environmental problems.
In a project sponsored by the DOE and operated by UOP LLC in collaboration with faculty from four different universities, MOFs were tested as possible carbon dioxide removal agents in post-combustion flue gas. They were able to separate 90% of the CO2 from the flue gas stream using a vacuum pressure swing process. Through extensive investigation, researchers found out that the best MOF to be used was Mg/DOBDC, which has a 21.7 wt% CO2 loading capacity. Estimations showed that, if a similar system were to be applied to a large scale power plant, the cost of energy would increase by 65%, while a NETL baseline amine based system would cause an increase of 81% (the DOE goal is 35%). Also, each ton of CO2 avoided would cost $57, while for the amine system this cost is estimated to be $72. The project ended in 2010,estimating that the total capital required to implement such a project in a 580 MW power plant was 354 million dollars.
Many other methods and materials have been discussed for scrubbing carbon dioxide.
- Regenerative carbon dioxide removal system (RCRS)
- Photosynthesis: e.g. Algae based carbon sink
- Polymer membrane gas separators
- Reversing heat exchangers
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