At Frontis Energy we have spent much thought on how to recycle CO2. While high value products such as polymers for medical applications are more profitable, customer demand for such products is too low to recycle CO2 in volumes required to decarbonize our atmosphere to pre-industrial levels. Biofuel, for example from field crops or algae has long been thought to be the solution. Unfortunately, they require too much arable land. On top of their land use, biochemical pathways are too complex to understand by the human brain. Therefore, we propose a different way to quickly reach the target of decarbonizing our planet. The procedure begins with a desired target fuel and suggests a microbial consortium to produce this fuel. In a second step, the consortium will be examined in a bio-electrical system (BES).
CO2 can be used for liquid fuel production via multiple pathways. The end product, long-chain alcohols, can be used either directly as fuel or reduced to hydrocarbons. Shown are examples of high level BEEF pathways using CO2 and electricity as input and methane, acetate, or butanol as output. Subsequent processes are 1, aerobic methane oxidation, 2, direct use of methane, 3 heterotrophic phototrophs, 4, acetone-butanol fermentation, 5, heterotrophs, 6, butanol direct use, 7, further processing by yeasts
Today’s atmospheric CO2 imbalance is a consequence of fossil carbon combustion. This reality requires quick and pragmatic solutions if further CO2 accumulation is to be prevented. Direct air capture of CO2 is moving closer to economic feasibility, avoiding the use of arable land to grow fuel crops. Producing combustible fuel from CO2 is the most promising intermediate solution because such fuel integrates seamlessly into existing urban infrastructure. Biofuels have been explored intensively in recent years, in particular within the emerging field of synthetic biology. However tempting the application of genetically modified organisms (GMOs) appears, non-GMO technology is easier and faster to implement as the required microbial strains already exist. Avoiding GMOs, CO2 can be used in BES to produce C1 fuels like methane and precursors like formic acid or syngas, as well as C1+ compounds like acetate, 2-oxybutyrate, butyrate, ethanol, and butanol. At the same time, BES integrate well into urban infrastructure without the need for arable land. However, except for methane, none of these fuels are readily combustible in their pure form. While electromethane is a commercially available alternative to fossil natural gas, its volumetric energy density of 40-80 MJ/m3 is lower than that of gasoline with 35-45 GJ/m3. This, the necessary technical modifications, and the psychological barrier of tanking a gaseous fuel make methane hard to sell to automobilists. To produce liquid fuel, carbon chains need to be elongated with alcohols or better, hydrocarbons as final products. To this end, syngas (CO + H2) is theoretically a viable option in the Fischer-Tropsch process. In reality, syngas precursors are either fossil fuels (e.g. coal, natural gas, methanol) or biomass. While the former is obviously not CO2-neutral, the latter competes for arable land. The direct conversion of CO2 and electrolytic H2 to C1+ fuels, in turn, is catalyzed out by electroactive microbes in the dark (see title figure), avoiding food crop competition for sun-lit land. Unfortunately, little research has been undertaken beyond proof of concept of few electroactive strains. In stark contrast, a plethora of metabolicstudies in non-BES is available. These studies often propose the use of GMOs or complex organic substrates as precursors. We propose to systematically identify metabolic strategies for liquid bio-electrically engineered fuel (BEEF) production. The fastest approach should start by screening metabolic databases using established methods of metabolic modeling, followed by high throughput hypothesis testing in BES. Since H2 is the intermediate in bio-electrosynthesis, the most efficient strategy is to focus on CO2 and H2 as direct precursors with as few intermediate steps as possible. Scalability and energy efficiency, economic feasibility that is, are pivotal elements.
First, an electrotrophic acetogen produces acetate, which then used by heterotrophic algae in a consecutive step.
Possible pathways for BEEF production involving Clostridium, 3, or heterotrophic phototrophs, 7, further processing by yeasts
Yeasts are among the microorganisms with the greatest potential for liquid biofuel production. Baker’s yeast, (Saccharomyces cerevisiae) is the most prominent example. While known for ethanol fermentation, yeasts also produce fusel oils such as butane, phenyl, and amyl derivate aldehydes and alcohols. Unlike ethanol, which is formed via sugar fermentation, fusel oil is synthesized in branched-off amino acid pathways followed by aldehyde reduction. Many enzymes involved in the reduction of aldehydes have been identified, with alcohol dehydrogenases being the most commonly observed. The corresponding reduction reactions require reduced NADH but it is not known whether H2 produced on cathodes of BES can be involved.
Clostridia, for example Clostridium acetobutylicum and C. carboxidivorans, can produce alcohols like butanol, isopropanol, hexanol, and ketones like acetone from complex substrates (starch, whey, cellulose, etc. ) or from syngas. Clostridialmetabolism has been clarified some time ago and is different from yeast. It does not necessarily require complex precursors for NAD+ reduction and it was shown that H2, CO, and cathodes can donate electrons for alcohol production. CO2 and H2 were used in a GMO clostridium to produce high titers of isobutanol. Typical representatives for acetate production from CO2 and H2 are C. ljungdahlii, C. aceticum, and Butyribacterium methylotrophicum. Sporomusa sphaeroides produces acetate in BES. Clostridia also dominated mixed culture BESs converting CO2 to butyrate. They are therefore prime targets for low cost biofuel production. Alcohols in clostridia are produced from acetyl-CoA. This reaction is reversible, allowing acetate to serve as substrate for biofuel production with extracellular energy supply. Then, energy conservation, ATP synthesis that is, can be achieved from ethanol electron bifurcation or H2 oxidation via respiration. While possible in anaerobic clostridia, it is hitherto unknown whether electron bifurcation or respiration are linked to alcohols or ketone synthesis.
Phototrophs like Botryococcus produce C1+ biofuels as well. They synthesize a number of different hydrocarbons including high value alkanes and alkenes as well as terpenes. However, high titers were achieved by only means of genetic engineering, which is economically not feasible in many countries due to regulatory constrains. Moreover, aldehyde dehydration/deformylation to alkanes or alkenes requires molecular oxygen to be present. Also the olefin pathway of Synechococcus depends on molecular oxygen with the cytochrome P450 involved in fatty acid decarboxylation. The presence of molecular oxygen affects BES performance due to immediate product degradation and unwanted cathodic oxygen reduction. In contrast, our own preliminary experiments (see title photo) and a corrosion experiment show that algae can live in the dark using electrons from a cathode. While the enzymes involved in the production of some algal biofuels are known (such as olefin and aldehyde deformylation), it is not known whether these pathways are connected to H2 utilization (perhaps via ferredoxins). Such a connection would be a promising indicator for the possibility of growing hydrocarbon producing cyanobacteria on cathodes of BES and should be examined in future research.
At Frontis Energy we believe that a number of other microorganisms show potential for BEEF production and these deserve further investigation. To avoid GMOs, BES compatible co-cultures must be identified via in silico metabolic reconstruction from existing databases. Possible inter-species intermediates are unknown but are prerequisite for successful BES operation. Finally, a techno-economical assessment of BEEF production, with and without carbon taxes, and compared with chemical methods, will direct future research.
Microbial electrolysis is a technology that uses living microorganisms as electro-catalysts in electrolysis cells. The technology can be used for wastewater treatment. Earlier, we proposed that microbial electrolysis be used to decentralize wastewater treatment and biogas production. Since this is a process that converts CO2 into organic compounds using electricity it can also be used for CO2 valorization. Besides methane, such electrolysis cells produce compounds such as acetic acid (vinegar), caproic acid, and others. It is then called microbial electrosynthesis.
However, the main problem with microbial electrolysis and electrosynthesis is the long start-up time. The start-up time is the time required for the microorganisms to form a biofilm on the electrode surface and to start producing the desired products. It can range from several weeks to several months, depending on the operating conditions and the type of microorganisms. This long start-up time limits the feasibility and the scalability of microbial electrosynthesis, as well as its economic and environmental benefits.
Now, scientists of the Wageningen University in the Netherlands presented new research, which aimed to reduce the start-up time of microbial electrosynthesis. By using a novel technique that involves alternating the direction of the catholyte flow through a three-dimensional electrode they were able to reduce the startup time to only ten days. They hypothesized that this technique enhances mass transfer and biofilm formation, and thus accelerates the CO2 reduction and the product formation. This was a start-up time reduction of 50%, compared to a conventional flow-through electrode.
The alternating electrolyte flow also reduced the power consumption to 136 kWh per kg of hydrogen. After 60 days, the local hydrogen concentration at the cathode was at a maximum of 600 μM, which indicates a better mass transport and thus a more active biofilm. The researchers speculated that the alternating catholyte flow improved mass transport, because the hydrogen could be better distributed over the cathode layers. In addition, the researchers think that alternating the flow refreshed potential “dead zones” in the cathode chamber.
However, there are limitations of the technique, such as the energy efficiency, the product selectivity, and the scalability of microbial electrosynthesis. Such limitations are typical for bench top experiments. We are therefore looking forward to see an industrial application of this new method.
Among others, the current European energy crisis was caused by a surge in demand after the pandemic, the embargo on Russia, the reluctance of investors to finance fossil energy projects and the throttling of production by the OPEC countries. In this complex situation, European countries are forced to develop alternatives and renewable energy sources. At the same time, however, natural gas is difficult to replace in many industries. One exception is the food and beverage industry, which sits enormous untapped resources of biogas in their wastewater.
Europe is the largest cheese maker in the world. More than 9 million tons of cheese are produced annually. With every ton of cheese, 9 m³ of cheese whey remain. Despite its high nutritional value, whey is often treated like wastewater for various reasons. Yet, the very high organic load in the whey makes it difficult to treat. Wasted whey can also be used for biogas production. In addition to whey, regular wastewater is also produced by cheese makers. For example, a medium-sized cheese factory pays 1.5 million euros a year for its waste water. Reducing these costs by producing biogas would turn dairy industry wastewater into a valuable resource.
This situation is similar in many other food and beverage sectors such as breweries, distilleries, winemakers, bakeries etc. All of these sectors have high energy requirements. Renewable electrical energy cannot meet this need. The market for wastewater treatment in Europe and the US is around 12 billion euros.
Traditional wastewater treatment is a cascaded process including aeration and anaerobic sludge digestion followed by incineration. These methods often consume more than 70% of the energy in a wastewater treatment plant. If contaminants such as high-energy total organic carbon or ammonia were converted into biogas before the process, at least 80% of the energy needed for wastewater treatment could be saved. It is absurd that this energy is removed from the wastewater using even more energy.
An ever-increasing number of sewage treatment plants already recover the resources contained in their wastewater, apart from the water itself. The oldest recivered products are biogas and fertilizers made from sewage sludge. Due to its heavy metal content such as copper and mercury, sewage sludge is no longer used as fertilizer but incinerated.
Biogas is particularly popular in Europe as the produced volumes and prices are high enough to compete with natural gas. Biogas is also a green alternative to natural gas as no additional CO2 is emitted. (Hence, it is often called Renewable Natural Gas in North America.) A disadvantage of classic biogas is the CO2 and sulfide content. Another disadvantage is that anaerobic digestion is the terminal treatment step, wasting valuable wastewater resources in the preceding treatment. Finally, the size and complexity of current digestion requires significant commitment from users when it comes to capital expenditures. Most food manufacturers prefer to focus on making food rather than cleaning their wastewater.
Novel high-performance biogas reactors solve these problems through miniaturization. A 20-fold size reduction is achieved compared to conventional systems. The new technology used was developed in Japan in the early 1990s and is called microbial electrolysis. The electrolysis of wastewater is catalyzed by electroactive microorganisms on the anode (the positive electrode). The reaction products are CO2 (from organic matter) and nitrogen gas (N2 from ammonia).
Principle of a microbial electrolysis reactor. On the left anode, the organic material is oxidized to CO2. The free electrons are absorbed by the anode and transported to the cathode. Hydrogen gas (H2) is released there. CO2 and hydrogen form methane, the final microbial reaction product.
At the same time, hydrogen gas (H2) is generated at the cathode (the negative electrode). This hydrogen reacts with CO2 to form methane. The final methanation step completes the biocatalytic treatment of the wastewater. Gas grid injection is one possible use. But for cheese makers, the gas would be used on site to generate electricity and/or heat.
The reaction is accelerated using an applied voltage and is based on the laws of thermodynamics. As a result, the reactor volume can be reduced. The size reduction has several advantages. First, it makes biogas accessible in markets where it was previously not possible due to the high investment costs. Second, it enables higher throughput at a lower cost. Smaller units are mobile and can be shared, moved or rented. After all, food manufacturers want to do what they do best, which is to make food.
An abandoned or unproductive oilfield can be reused for methane production from CO2 using renewable electrical power. Exhausted oilfields can be reactors for the conversion of renewable energy to natural gas using microbes. To achieve this, an oilfield can be made electrically conductive and catalytically active to produce natural gas from renewable power sources. The use of natural gas is superior to any battery because of the existing infrastructure, the use in combustion engines, the high energy density and because it can be recycled from CO2. Oilfields are superior to any on-ground production because of the enormous storage capacities. They are already well explored and these geological formations underwent environmental risk assessments. Lastly, the microbial power-to-gas technology is already available.
Process summary
Whole process (end-to-end via methane)
50% electrical efficiency
Energy density of methane
180 kWh kg−1
Storage capacity per oilfield
3 GWh day−1
Charge/Discharge cycles
Unlimited
Investment (electrodes, for high densities)
$51,000 MW−1
Cost per kWh (>5,000 hours anode lifetime)
<$0.01 kWh−1
Electrolyte
Seawater
The Problem
To address the problem of storing renewable energy, batteries have been proposed as a possible solution. Lithium ion batteries have a maximum energy storage capacity of 0.3 kWh kg−1. To date, this is considered the best trade-off between cost and efficiency but these batteries are still too inefficient to replace gasoline, which has a capacity of about 13 kWh kg−1. This makes battery driven cars heavier than conventional cars. Lithium air batteries are considered a possible alternative because they can reach theoretical capacities of 12 kWh kg−1 but technical difficulties have prevented them from being used for transportation.
In contrast, methane has an energy density of 52 MJ kg−1 corresponding to 180 kWh kg−1 which is second only to hydrogen with 500 kWh kg−1, not counting in nuclear energy. This high energy density of methane and other hydrocarbons along with their facile usage, is the reason why they are used in combustion and jet engines that drive nearly all transportation to date. While electrical cars seem to be a tempting green alternative, the fact that combustion engines and the fueling infrastructure are so wide-spread makes it difficult to switch.
In addition to the difficulty of changing habits, battery-driven electrical cars need other limited natural resources such as lithium. To equip all 94 million automobiles produced worldwide in 2017, 3 mega tons lithium carbonate would need to be mined annually. This is nearly 10% of the entire recoverable lithium resources of 35 mega tons worldwide. Although lithium and other metals can be recycled, it is clear that metal based batteries alone will not build the bridge between green energy and traditional ways of transportation due to the low energy densities of metals. And this does not even take into account other energy demands such as industrial nitrogen fixation, aviation or heating.
For Germany, with its high proportion of renewable energy, fuel for cars is not the only problem. As renewable energy is generated in the north, but many energy consumers are in the south, the grid capacity is frequently reached during peak production hours. A steadier energy output can only be accomplished by decentralizing the production or by energy storage. To decentralize production, homeowners were encouraged to equip their property with solar panels or windmills. As tax incentives phase out, homeowners face the problem of energy storage. The best product for this group of customers so far are again lithium ion batteries but investment costs of $0.10 kWh−1 are still unattractive especially because these products store the energy as electricity which can only be used for a short time and is less efficient than natural gas when used for heating.
Natural gas is widely used as energy source today and the global energy infrastructure is designed for natural gas and other fossil fuels. Increasing demand and limited resources for these fossil fuels were the main drivers of oil and gas prices during the last years, slowed by the recent economic crises and hydraulic fracturing (fracking). The high oil price attracted investors to recover oil using techniques that become increasingly expensive and are environmental risks such as deep-sea drilling or tar sand extraction. Ironically, the high oil price made costly renewable energies an economically feasible alternative and helped driving down their cost. Since habits are difficult to change and building an entirely new infrastructure only for renewable energies does not seem economically feasible today while CO2 drives global warming, a more realistic solution needs to be found.
Microbial Power-to-Gas could be a bridging technology that integrates renewable energy into the existing fossil fuel infrastructure. It reaches break even in less than 2 years if certain preconditions are met. This is accomplished by integrating methane produced from renewable energy into the current oil and gas producing infrastructure. The principal idea is to use carbon instead of metals as energy carrier because of its high energy density when bound to hydrogen. The benefits are:
High energy density of 180 kWh kg−1 methane
Low investments due to existing infrastructure (natural gas, oilfield equipment)
Carbon is not a limited resource
Low CO2 footprint due to CO2 recycling
Methane is a transportation fuel
Methane is the energy carrier for the Haber-Bosch process
Inexpensive catalysts further reduce initial investments
Low temperatures due to bio-catalysis
No toxic compounds used
No additional environmental burden because existing oilfields are reused
The solution
Methane can be synthesized by microbes or chemically. Naturally, methane is produced by anaerobic (oxygen-free) microbial biomass decomposition. The energy for biomass synthesis is provided by sunlight or chemical energy like hydrogen. In the case of methanogens (methane producing microbes), energy is harvested after CO2 and hydrogen were released from biomass decomposition following a 1-to-4 stoichiometry:
CO2 + 4 H2 → CH4 + 2 H2O
Without microbes, methane is produced by the Nobel-prize winning Sabatier reaction and several attempts are currently underway to use it on industrial scale. It is necessary to split water into hydrogen and use this to reduce CO2 in the gas phase. A major drawback of the Sabatier reaction is the need for high temperatures around 385ºC, and a nickel catalyst that becomes quickly spent. Methanogens use iron-nickel enzymes called hydrogenases to harvest energy from hydrogen, but do so at ambient temperatures.
Power-to-Gas concept for exhausted oilfields. Electrolysis catalyzes water splitting inside the oilfield producing methane gas and O2.
The future challenge will be to accelerate methane production rates as has been reported for a high temperature oilfield cultures. Besides increasing the temperature, the most obvious solution is to use a higher reactive surface and bringing both electrodes closer together. Using carbon brushes that are poor hydrogen catalysts but provide a higher surface for microbial attachment is one possibility. Methane production correlates with microbial cell numbers in the reactors.
The number of methanogens in microbial electrolysis reactors correlates with the electrode surface.
To overcome the problem of expensive carbon (and also steel) brushes for large scale applications,exhausted gas and oilfields could be used. They provide a high surface area and are usually economic liabilities and not assets. Methanogens inhabit oilfields where they carry out the final step in anaerobic petroleum degradation. Hence, oilfields can be seen as bioreactors at geological scale. Geological formations provide ideal conditions for producing, storing and extracting methane.
Open questions and potential solutions
Oilfield porespace volume
The Californian Summerland oilfield, for instance, has been abandoned and extensively studied in the past. It produced 27 billion barrels of oil and 2.8 billion m3 methane during its lifetime of 90 years. This maximum load of 3.5 billion m3 left the same volume of porespace filled with seawater behind. Only 2% of these pores are larger than 50 µm, which is necessary for microbial growth assuming dimensions of 1 x 2 µm of a methanogen cell. Experiments showed that the resulting 70 million m3 accessible porespace have a storage capacity of 35,000 TW. That is a lot of methane assuming a solubility of 0.74 kg methane m−3 seawater at 500 m water depth. All German off-shore windfarms together have a capacity of 7,000 MW. Obviously, the limiting factor is not the volumetric storage capacity of an oilfield.
Microbial methane production rates
But how fast can microbes produce methane in an hypothetical oilfield? Under optimal conditions, methanogens that grow on electrodes (typically the genus Methanobacterium or Methanobrevibacter) can produce methane at a rate of 100-200 nmol ml−1 day−1 (equals 2.24-4.48 ml l−1 day−1) depending on catalyst and potential. Using a production rate of 15 J ml−1 day−1 of methane (190 nmol ml−1 day−1), the entire microbially accessible oilfield (2%) has a capacity of 3.6 million MBtu per year. Microbes would theoretically consume 1 TWh per year for 3.6 million MBtu methane production if there were no losses and electrical power is translated into methane 1-to-1. A power generator of 121 MW would be sufficient to supply the entire oilfield at these rates. However, all German off-shore windfarms produce 7,000 MW meaning that only 3% off-peak power can be captured by our example oilfield. Therefore, the catalytic surface and activity must be increased to accelerate methane conversion rates.
Since methanogens produce methane from hydrogen, not only the 2% porespace big enough for cells can be used resulting in an increased catalytic surface to nearly 60%. A hydrogen catalyst needs to be found that does not out-pace methanogen growth to keep the reservoir pH within the limits of 6-8 required for methanogen growth. This hydrogen catalyst must be cheap and render an oilfield electrically conductive. A chemical formulation that mimics microbial hydrogen catalysis could be used. It has the potential to turn a non-conductive and non-catalytic oilfield into a conductive hydrogen catalyst sufficient to sustain methane production needed to store all of Germany’s electricity produced by off-shore windfarms. This catalyst is soluble in water when inactive. To become active, it coats mineral surfaces by precipitation that can be triggered by indigenous microbes or by electrical polarization. The investment would be $2.3 million per MW storage capacity ($16 billion for the entire 7,000 MW). Due to microbial growth, the catalytic activity of the system improves during operation and there is no need for the second component if an immediate production is not crucial. The investments made on the cathode side would then be as low as $600 per MW ($4.2 million for 7,000 MW).
Anodes
As the cathodic side of the reaction can be excluded as limiting factor, the anode needs to be designed. Several commercially available anodes such as mixed metal oxides (up to 750 A m−2) with platinum on carbon black or niobium anodes (Pt/C, 5-10 kA m−2) could be used. Anodes based on platinum are the most cost-efficient material available on the market. Investments made for Pt/C (10%, 6 mg cm−2) anodes will amount to $50,000 per MW ($350 million for 7,000 MW). However, the exact amount of Pt needed for the reaction still needs to be evaluated in an experiment because the corrosion rate at 2 V cell voltage is unknown. An often cited value for the lifetime of fuel cells is 5,000 hours and is used here to determine the costs per kWh. For 5,000 hours lifetime, the costs per kWh will be at the targeted limit of $0.01 but may be well below that because Pt/C anodes can be recycled and the Pt load may be reduced to 3 mg cm−2 (5%). Alternatively, steel anodes (SS316, 2.5 kA m−2, $54,000 per MW) can be used but it is unclear when steel anodes fail to electrolyze. In conclusion, the anodic side is the cost-driving factor. Hopefully, better water splitting anodes will lower these costs in future.
Cost estimation summary
Windfarms
Already in place
CO2 injection
Already occurred
Natural gas capturing equipment
Already in place
Microbial seed
Wastewater from oil rig
Cathode costs
$600 MW−1
Anode costs
$50,000 MW−1
Electrolyte (seawater)
Free
Total (>5,000 hours anode lifespan)
<$0.01 kWh−1
Energy and conversion efficiencies
The whole cell voltage for microbial power-to-gas reactions varies from 0.6 to 2.0 V, depending on cathodic rates, anodic corrosion and the presence of a membrane. Higher voltages will accelerate anode corrosion, again, making anodes the limiting factor. As the voltage decreases, methane production rates become slower but also more efficient. The voltage also depends on the pH of the oilfield. An oilfield that underwent CO2 injection as enhanced recovery method will have a low pH, providing better conditions for hydrogen production but not for microbial growth and must be neutralized using seawater. As stated above, the oilfield, being the cathode, is not limiting the the system. The use of Pt/C anodes eliminates the overpotential problem on the anode side. Hence, we can assume an ideal system that splits water at 1.23 V. However, the voltage is often 2 V due to anode and cathode overpotentials. Optimized cultures and cathodes produce about 190 nmol ml−1 day−1 methane which equals 0.15 J ml−1 day−1 using the energy of combustion of 0.8 MJ mol−1. The same electrolysis cell consumes 0.2 mW at a cell voltage of 2 V which equals 0.17 J ml−1 day−1 and the resulting energy efficiency is 91%. The anodes can be simple carbon brushes and the two chambers of the cell are separated by a Nafion™ membrane. The system can still be optimized by using Pt/C anodes and by avoiding membranes.
The overall electricity-methane-electricity efficiency also depends on the consumption side efficiency where methane is used in combustion engines and gas fired power plants. Such power plants frequently operate at efficiencies of 40- 60%. Assuming a reasonable power efficiency of 80% (see above), the overall electrical power recovery using gas fired power plants will be up to 50%. Besides the high efficiency of gas fired power plants, they are also easy to build and therefore contribute the a better power grid efficiency. Coal fired power plants can be upgraded to gas fired power plants.
Experimental approach
The conversion efficiencies of charge (Coulombs) transported across the circuit are usually between 70-100% in these systems depending on the electrode material. Another efficiency limitation could arise from mass transport inhibition. Mass transport can be improved by pumping electrolyte adding more costs for pumping which still have to be determined. However, since most oilfields undergo seawater injection for enhanced oil recovery the additional cost may be negligible. The total efficiency has yet to be determined in scale-up experiments and will depend on the factors mentioned above.
The reactor simulates oilfield conditions using sand as filling material under continuous flow of electrolyte.
Controlling the pH is crucial. Alkaline pHs significantly impede hydrogen production and therefore methanogenesis. This can be addressed by a software that monitors the pH and adjusts the potential accordingly. Addition of acids is not desired as this drives the costs. The software can also act as potentiostat that then fully controls the methane production process. To test the process under more realistic conditions, a drill core from an oilfield must be obtained.
Results show methane production in the simulation reactor. The appearance of methane in the anode compartment was a result of flow from the cathode to the anode, carrying produced methane with it.
Return of investment of the microbial power-to-gas process
The the microbial power-to-gas process in unproductive oilfields is economically superior to all other storage strategies because of the low start-up and operating costs. This is achieved because the major investments are the installation of oil- and gas production equipment and renewable power plants which are already in place as a precondition. These investments break even in a short amount of time.
But how can the microbial Power-to-Gas process accelerate the return of investment in renewable energy? Only 8 out of 28 active off-shore windfarms reported their investment costs. These 8 produce roughly half the overall power of 1,600 MW corresponding to $7 billion. While the maximum production of an oilfield with unlimited supply of electricity would yield hypothetical 3.6 million MBtu natural gas per year resulting a return of $13 million per year the real production is limited by off-peak power generated by renewable energy production. Assuming that the maximum annual methane production corresponds to 10% excess electrical power, $15 million per year can by generated by selling 4.3 million MBtu methane per year on the market. These are $15 million that are not lost during off-peak shutdowns. Clearly, this conservative estimate can help to compensate the investment in renewable energy earlier. It also decreases the investment risk because the investment calculations for new wind farms can be made on a more reliable basis.
In the example using all German windfarms (7,000 MW) this compensation roughly doubles. Using the $60 million generated by methane sales per year, the investment of $4 million for the cathodic catalyst and the $36 million for the Pt/C anodes are compensated for within less than a year. No other investments are required because the target oilfield already produced oil and gas and all necessary installation are in working condition. The target oilfield is swept using seawater as secondary extraction method. Electrical installations are in place for cathodic protection of production equipment in order to prevent microbial corrosion, which, however, may need to be upgraded to pass the now higher power densities. Moreover, CO2 is used from CO2 injection as tertiary enhanced oil recovery method. Only the pH may then need to be adjusted to sustain life by sweeping with seawater.
And this is not the end of oilfield storage capacity. In theory, an oilfield can store the entire amount of renewable energy produced in one year globally, allowing more than enough head room for future development and CO2 sequestration.
In our last post on water quality in China, we pointed out a study that shows how improved wastewater treatment has a positive effect on the environment and ultimately on public health. However, wastewater treatment requires sophisticated and costly infrastructure. This is not available everywhere. However, extracting resources from wastewater can offset some of the costs incurred by plant construction and operation. The question is how much of a resource is wastewater.
A recent study published in the journal Natural Resources Forum tries to answer that question. It is the first to estimate how much wastewater all cities on Earth produce each year. The amount is enormous, as the authors say. There are currently 380 billion cubic meters of wastewater per year worldwide. The authors omitted only 5% of urban areas by population.
The most important resources in wastewater are energy, nutrients like nitrogen, potassium and phosphorus, and the water itself. In municipal wastewater treatment plants they come from human excretions. In industry and agriculture they are remnants of the production process. The team calculated how much of the nutrient resources in the municipal wastewater is likely to end up in the global wastewater stream. The researchers come to a total number of 26 million tons per year. That is almost eighty times the weight of the Empire State Building in New York.
If one would recover the entire nitrogen, phosphorus and potassium load, one could theoretically cover 13% of the global fertilizer requirement. The team assumed that the wastewater volume will likely continue to increase, because the world’s population, urbanization and living standards are also increasing. They further estimate that in 2050 there will be almost 50% more wastewater than in 2015. It will be necessary to treat as much as possible and to make greater use of the nutrients in that wastewater! As we pointed out in our previous post, wastewater is more and more causing environmental and public health problems.
There is also energy in wastewater. Wastewater treatment plants industrialized countries have been using them in the form of biogas for a long time. Most wastewater treatment plants ferment sewage sludge in large anaerobic digesters and use them to produce methane. As a result, some plants are now energy self-sufficient.
The authors calculated the energy potential that lies hidden in the wastewater of all cities worldwide. In principle, the energy is sufficient to supply 500 to 600 million average consumers with electricity. The only problems are: wastewater treatment and energy technology are expensive, and therefore hardly used in non-industrialized countries. According to the scientists, this will change. Occasionally, this is already happening.
Singapore is a prominent example. Wastewater is treated there so intensively that it is fed back into the normal water network. In Jordan, the wastewater from the cities of Amman and Zerqa goes to the municipal wastewater treatment plant by gravitation. There, small turbines are installed in the canals, which have been supplying energy ever since their construction. Such projects send out a signals that resource recovery is possible and make wastewater treatment more efficient and less costly.
The Frontis technology is based on microbial electrolysis which combines many of the steps in wastewater treatment plants in one single reactor, recovering nutrients as well as energy.
During the last decades, China has achieved rapid development in technology and economics, however at a huge environmental cost. The deterioration of inland surface water quality is considered one of the most serious environmental threats to ecosystem and ultimately public health.
Since 2001, China made major efforts to tighten the application of environmental rules in order to stop water pollution emitted by cities, farm and industry. According to the government’s “10th National Five-Year Plan”, large investments were made for pollution control and wastewater discharge regulation systems.
Small research studies showed that with this campaign, Chinese’s lakes and rivers got cleaner. Since then water quality has improved significantly − however, other parts of country still have problems with polluted water.
Now, a team of researchers of the at the Chinese Academy of Sciences in Beijing, has published one of the most comprehensive national investigation of China’s surface water quality in the renown journal Science. The researchers investigated all regions of the country to learn how surface water responds to multiple driving forces over time and space. Their report covers the assessment of water quality by means of three parameters: dissolved oxygen level (DO), chemical oxygen demand (COD) and ammonium nitrogen (N) in inland surface waters. They performed monthly site-level measurements at major Chinese rivers and lakes across the country between 2003 and 2017.
Due to regional variations in China’s inland water quality as well as the dynamics in multiple anthropogenic pollution sources, such studies are crucially important to identify the necessary regulation measures and water quality improvement policies adapted to ecosystem sustainability at all diverse country regions.
The results show that during the past 15 years, annual mean pollution concentration has declined across the country at significant linear rates or was maintained at acceptable levels. Consequently, the annual percentage of water quality have increased by 1.77% for COD, 1.83% for N and 1.45% for DO per year. While China has not yet implemented environmental water standards, the study shows that China’s water quality is improving nonetheless.
The best news is that the notoriously high pollution levels have declined as cities and industry have worked to clean up and reduce their discharges. According to the authors, the most visible alleviation was noticed in northern China, while in the western region of the country water quality remained at their low pollution level throughout the observation period. The reason is likely that pollution is caused by human activity, of which there is less in those parts of the country.
Despite large efforts toward decreased pollution discharges, urban areas are still considered as the major pollution centers. These areas face additional pressure due to the constant migration and fast urbanization of the rural regions. Especially in northern China, with high-density human activity and exploding urbanization, achieving and maintaining a clean environment is a permanent struggle.
To further reduce pollution and improve water quality, the authors recommend that future activities focus on water management systems and the water pollution control. For both, the central government issued guidelines to control and improve water use and pollution discharge at regional and national levels for 2020 and 2030.
At Frontis Energy, we certainly support activities in China that help improving the countries water quality and public health. The Frontis technology gives its user an incentive to to clean wastewater before discharge by extracting its energy. Our patentpending solutions are based on microbial electrolysis which helps to extract energy from wastewater and apply in particular to China.
How do we shape human exploration on Mars to minimize what we must bring with us and to maximize the value and utility of what we bring, and augment it with what is already there?
To provide sufficient fuel for a safe return of the Mars crew, we can produce methane and oxygen on Mars which could be aided by microbes that are brought to Mars. We suggest lightweight perovskite solar panels that may be transported to Mars. In the optimistic scenario, about 18 months are required for the installation of surface solar power and fuel production for the failsafe return after which the crewed mission commences. The pessimistic scenario takes 4 years. To save oxygen, we also suggest Martian perchlorates as rocket fuel component. For later missions’ food supply, we suggest to use lichens as primary colonizers to produce organic rich soil.
Procedure to produce energy on Mars
We suggest the use of in situ Martian resources for the production of methane as ascent and return propellant. Since oxygen generated during electrolysis is not sufficient for a safe return, we also suggest to use algae for the production of oxygen. Algal biomass will be used as soil for food production. Methane producing microbes will be contained in methanogenic electrolysis reactors (MER) while algae will grow in covered craters. The production of methane on Mars is to be carried out autonomously by robots and reactors that will land near the ice-rich polar regions to melt water as electrolyte for low temperature electrolysis. The Mars lander will autonomously construct facilities with the purpose of propellant production to fuel the Mars transfer vehicle which enables transport between Mars surface and Earth orbit. Only when enough propellant for a safe return to Earth has been produced, shall a manned Mars mission begin. Furthermore, methane will be used as energy storage should there be failure of energy collectors such as solar panels. Goal is to erect a 3.5 MW solar power plant on Mars by the end of the first manned mission.
Schematic of the fuel production process. Red circles highlight the end products steel (top) and CH4/O2 (bottom). Top: 1, Lander on ice, 2, Nuclear fission reactor (NFR) with heat exchanger to melt ice, 3, mining unit, 4, iron/nickel ores, 5, induction steel foundry with energy supply from the NFR (2), 6, algae enrichment tank with water supply from the NFR (2), 7, crater algae reservoir producing O2 and biomass for 8, dehydrator separating water and 9, biomass pellets, 10, carbon steel for Bottom: 11, solar heat collector melting ice and producing water for 12, microbial electrolysis reactor (MER) producing methane and oxygen collected by 13, degasser, 14, solar panels mounted on carbon steel producing electricity for MER (11), 15, gas storage tank, 16, Mars orbit transfer vehicle fueled by CH4/O2
To sustain the life of 6 crew members a power production capacity of 170 kW (see “Surface habitat energy needs”) is required and has highest priority along with fuel production for a safe journey home. The procedure is sketched out in the figure above. It is a stepwise process during which most steps are interdependent and therefore self-accelerating as power production increases. To minimize risk of failure, we recommend at least four independent landers in the circum-polar region of Mars. The polar regions bear the highest surface water content which is crucial for manned explorer missions, methanogenic electrolysis as well as the production of oxygen and biomass. The landers will carry a small nuclear fission device that will begin mining for iron and titanium ores to produce the steel required as structural support for solar panels. First, the lander begins mining for iron ores so that steel production can begin. Graphite or other reduced forms of carbon for steel production will be shipped from Earth because organic matter production on Mars by algae is a slow process. Alternatively, lightweight modular carbon fiber elements to mount solar panels will be brought from Earth to Mars. Once the 170 kW solar plant is established, melting ice for the methanogenic electrolysis reactors (MER) begins. Combined power from the nuclear fission reactor (NFR) and the solar plant will be used. Only when the amount of methane for a failsafe return (Orion capsule size) has been produced, power will be diverted into three equal parts: continue to melt ice for algae, start or continue to mine ores for thermal collectors, continue to produce methane. After enough thermal collectors are produced to pace ice melting with algal growth, electrical ice melting will be shut off. Now, electrical energy is used for steel production to install more solar panels and methane production until sufficient for a comfortable (more payload) return. By this time, the crew is arriving and decides what the highest priorities are. We recommend to focus on accelerating algal growth for oxygen and biomass production as complete independence from Earth requires the production of organic carbon from CO2.
The composition of Martian soil as analyzed by NASA’s Curiosity and other rovers (Source: NASA 2012)
Energy need for the Mars Transfer Vehicle
Fuel produced on Mars will serve 3 purposes:
Failsafe: return of one Orion-sized vehicle
Desired: production of return fuel allowing for less stress (more comfort) during transit
Energy storage at night or power failure
Two options for Mars-Earth return seem possible. (1) Option one was suggested by NASA’s DRA 5.0 and involves one Orion-like vehicle of about 12 tons and a travel speed of 14 km/s. This option requires only one vehicle but provides less comfort for the long journey home and hence, it exposes the crew to higher stress. However, it uses less fuel therefore enables a faster completion of the first Mars mission. (2) We envision a second option that involves two vehicles, one Orion-like lift-off vehicle for transport of 6 crew members into a Mars orbit of 250 km and one transit vehicle to return to Earth. As option two is the preferred option, we recommend to use option one, the Orion-only scenario, as failsafe scenario.
We assume the capacity of a manned Orion capsule with Dragon thrusters (Draco) as reference. The Orion-sized vehicle can carry 6 crew members and has a weight of 12 tons including fuel. For a Mars lift-off, a thrust-mass ratio of at least 5 N/kg will be needed resulting in 60 kN thrust or 150 Draco thrusters to lift 6 crew members. The travel time from Martian surface to a 250 km orbit would be 7 minutes at full thrust. About 600 m3 methane (at Earth atmospheric pressure) would be required for the lift-off. To produce this amount of methane at 210 kW (40 kW nuclear fission and 170 kW solar power, see “Surface habitat energy needs”), 3 years of dedicated fuel production are necessary. The proposed solar power installations of 1,400 m2 perovskite solar cells can produce effectively 170 kW during a Mars day of 8h (that is, 20 kW/m2 can be captured by perovskite panels). Using the same Orion capsule also for the Mars-Earth transit, another 7 minutes or 17,000 km are required to reach the travel speed of 14 km/s and approximately the same for full stop. To produce enough fuel for the Mars-Earth transit, only 3 more days are required. Once enough fuel for the failsafe scenario has been produced, the crew will leave the lower Earth orbit heading for Mars.
For the comfort scenario, we assume the proposed 63-ton crewed payload option from the Mars DRA 5.0 used for Earth-Mars transit. This seems reasonable as most equipment will be left behind on Mars and only the transit habitat, the Orion capsule (for emergencies), engines and fuel are needed. This scenario, however, requires considerably more fuel for which the 210 kW surface power generators must produce methane for at least 42 years. Since this is out of scope, we recommend an extension of the surface power production to 3,500 kW which would reduce the required production of methane to 30 months at 14 km/s travel speed or 12 months at 9 km/s. The reduced stress on the crew justifies the lower travel speed and the higher investment. However, 6.3 tons (corresponding to 0.18 km2) of perovskite solar panels will be required to produce sufficient fuel. About 280 tons of steel are necessary as structural support for this scenario. Since 900 kWh/ton of steel will be consumed for electric smelting, only about one year of steel production using a 40 kW NFR (or 2 months using the full combined 210 kW) justify the increased comfort. The shipment of carbon fiber elements form Earth may completely eliminate the need for steel production in this stage of the mission. The process will be self-accelerating as power production increases during the solar panel assembly process.
To produce methane sufficient for one lift-off, a 200,000 liter MER is required using steel mesh/brush electrodes (anode and cathode) of 2,200 m2 projected surface (see figure below). A modular redundancy system of smaller dimension will improve safety but requires more material. MERs have the theoretical capacity to produce sufficient ascent fuel for one Orion capsule within less than one or two days, if power supply were sufficient. At maximum performance, this reactor would consume about 100 GWh or 220 kWh/mol methane. Microbes will facilitate electrolysis at low temperatures and these microbes will be carried by the Mars lander in small (100 mL) redundant batches. Since the limit for methane production is not the reactor capacity but the electrical power available, doubling the amount of solar panels will half the time required for methane production and so on. To store the so produced methane we recommend to first pressurize water to 200 bar before it is injected into the MER. To extract as from the electrolyte, a small pressure reduction is needed and the so obtained gas phase is then conducted into pressurized steel tanks for later use.
An experimental MER needs to be constructed on Earth to prove this concept. Like the Mars reactor, this experimental MER will be a 5 x 5 m cylindrical reactor of either one or two chambers each. The advantage of the two-chamber system is the separation of oxygen and methane but it requires more water while the single chamber reactor is easier to build and holds less water but O2/CH4 separation is required after production. Unfortunately, the ratio of oxygen to methane is difficult to predict as it depends on the anodic pH. A mass ration greater than 2:1 is required. We therefore propose the use of algae as additional oxygen source (see “Photosynthesis crater to produce oxygen and biomass”). As electrodes brush or spiral steel mesh electrodes will be used. Steel mesh (40 x 40 mesh) produced on Mars will be used having a 1,100 m2 projected surface of each electrode.
A detailed description of the reactor can be found here.
Alternative oxidants in cold methane fuel cells or rocket fuel
It is anticipated that oxygen scarcity imposes severe limitations on any manned Mars mission. Oxygen is crucial as propellant and for any human presence. The use of methane for energy storage makes only sense if there is an adequate electron acceptor. While methane can be burnt in turbines at acceptable efficiencies for electricity production, it may also be used in fuel cells. However, no catalysts exist that oxidize methane on electrodes at room temperature or below. The only possible exception are anaerobic methane oxidizing consortia that naturally use biological electron transport chains. The use of biological electron transport chains opens the possibility to capture the energy stored in electrons during transport. Since this is electron acceptor independent, oxidized metal minerals, which are abundant on Mars, can be used as electron acceptors. The disadvantage of this methane fuel cells is that less energy will be captured compared with oxygen. Also, they only exist in theory.
The high acidity on Mars, however, is in favor of reaction, forming additional water from iron oxides and protons using the reductive power of methane. Soluble Fe2+ may be used for electric steel production as the reduction of Fe2+ to Fe0 requires a considerably lower redox potential and therefor lower energy.
Martian perchlorate salts may serve as oxidant in rocket fuel. Ammonium perchlorate and, on Mars, the more prevalent calcium perchlorate are explosive oxidizers. To transform calcium perchlorate into the ammonium salt, ammonium can be produced by a variety of microbial process such as nitrogen fixation (by way of the nitrogenase enzymes) and catabolic ammonification of amino acids or waste urea (by the urease enzyme). Should collection and compression of the photosynthetically derived O2 gas prove impractical for in rocket fuel, our solid oxidizer approach is also submitted. This dual oxidizer strategy will provide for far greater flexibility and more breathable oxygen. Mined perchlorate may also be used to disinfect water.
Photosynthesis crater to produce oxygen and biomass
Oxygenic biophotolysis of water using psychrophilic (cold-loving), dinitrogen fixing cyanobacteria, i.e. blue green algae, grown in covered craters is one proposed plausible means of generating the need for oxygen and biomass. The surplus of oxygen will be required as propellant and component of artificial air in the surface habitat (SHAB). While initially not crucial for a Mars mission, the production of organic matter is useful for more extended missions with larger teams and longer presence. Organic matter is essential for rich soil which, in turn, is pivotal for vegetable food production on Mars. Moreover, cyanobacteria and algae require little engineering and energy which makes them ideal for autonomous production of utility compounds such as organic matter and oxygen.
The amount of damaging cosmic rays and UV can be higher due to the lack of an ozone layer and protective magnetosphere. The amount of cosmic radiation (est. 0.076 Grays per year) is certainly within the tolerable range for many Earthly microbes as it is only around what the interior of the international space station is exposed to. UV light, with its shorter wavelength, can be readily blocked by a thin covering of Martian soil whereas longer wavelengths of photosynthetically active radiation can penetrate further. The microbes will be selectively enriched in their survival zones. Alternatively, a UV protective cover could be used over the crater. The lightweight but durable and robust crater coverings could take the form of an inflatable inverted dome anchored around the crater edge by cables and spikes. The clear upper canopy would admit sunlight but have coating to block harmful radiation while the curved lower surface could be reflective (to maximize photosynthesis) or black to absorb heat. Solar powered gas pumps could adjustably increase the internal gas pressure to accelerate carbon and nitrogen fixation rates and water accumulation from the trace water vapor available.
Conversion of limited amount of solar energy and frozen water plus copious CO2 into biologically generated oxygen plus organic matter will require a phototroph capable of survival at extremely low temperatures consistent with the Martian surface. We propose to identify terrestrial cyanobacteria capable of this by selectively enriching them from mixed biofilm consortia obtained from the Earth’s Arctic and Antarctic regions. Samples obtained from rocky coastal brines will be subjected to intensive evaluation in selective enrichment freezers outfitted to replicate the polar Martian habitat. The finding that the lichen Pleopsidium chlorophanum (gold cobblestone lichen) can survive, adapt and grow under Martian environmental conditions bodes well for this approach.
During the initial surface resource utilization phase (see figure above), the growth of algae is the most time consuming step and therefore the production of liquid water has highest priority. The use of craters will eliminate the need for containers for growing and there reduce the amount of material brought to Mars. Ideally, such craters are equatorial flat water ponds that ensure maximum sunlight capture and minimum water reheating. These preconditions do not align with the initial mission setup (landing near polar ice caps) but should be prepared during the first mission. That is, water pipes from the circum polar regions to the equatorial areas must be constructed. The pipes may need to be heated which requires additional energy or heating the melted water to high temperatures and pressures to prevent ice formation during transport.
Production of water as medium for methanogenic electrolysis and algae
The lack of liquid water is a major hindrance since active metabolism requires a fluid aqueous medium. In addition to the production of methane fuel, melting ice is the greatest challenge for the first manned Mars mission. Liquid water is essential for MERs and algae craters. Hence, all excess of heat or electrical power produced should be directed to melting of ice after methane fuel production is secured. The obtained CO2-rich brine is the electrolyte for MERs. The high acidity is not inhibitory for microbial growth as acidophilicmethanogens and algae were reported from terrestrial environments. Fortunately, the low pH will reduce the electrical overpotential needed for hydrogen generation, which is the intermediate step during methanogenic electrolysis. The low pH, on the other hand, inhibits oxygen formation which is why corrosion of steel anodes is anticipated to become a possible problem. Anode corrosion must be monitored and shall not exceed a certain, yet to be determined, threshold before spent anodes are recycled in steel foundries brought with the first mission.
The low temperatures on Mars that reach only 20°C in equatorial regions also impose a major hurdle on liquid water maintainance. That is, water may need to be heated by parabolic heat collectors to remain liquid. However, Fischer et al. recently found that “when the salts are in contact with water ice, liquid brine forms in minutes, indicating that aqueous solutions could form temporarily where salts and ice coexist on the Martian surface and in the shallow subsurface.” If our crater canopy is fitted with an internally reflective coating in the infrared spectrum small green houses can be created an the brine will remain liquid longer.
The MERs use methanogenic microorganisms for methane production which will be brought to Mars along with algae seeds by the landers. The methanogenic microbes are highly efficient in methane production, resulting in electricity capturing efficiencies close to 100%. Precious metal catalysts are not required. In contrast, for effective oxygen production, platinum or palladium coating may be required on the anodic side of the MERs. Anodic algae appear to be an alternative but need to be further explored. Since the amount of platinum used is very low, it may be transported as salt to Mars and electroplated on steel electrodes once they are ready. Electroplating is an easy procedure so that a robot can accomplish this task within few minutes. However, platinum recycling requires 1-2 days of work of one crew member.
About 280 tons of steel for structural support of solar panels are required (see “Production of steel for structural support of Mars surface components”). The carbon content of steel should not exceed 2.1% to guarantee high stability and therefore we chose 1.5% carbon for Mars steel. That is, about 4 metric tons of carbon are required for steel production. This is the bottleneck of steel production. Assuming cold conditions on Mars comparable to the Antarctic, a good approximation for biomass concentration in brine is 5 mg/m3. At this concentration, nearly 1 billion m3 water need to be processed. While the existing amount of 821,000 km3 would be more than sufficient, it is impossible to melt this amount of ice within the mission’s timeframe using an NFR of 40 kW even if other power sources were counted in. Therefore, parabolic heat collectors could be shipped from Earth as well. At an energetic efficiency of parabolic heat collectors of 80%, 300 tons would be required to melt this amount water within 2 years. Using 10 tons of parabolic collectors, one can melt only 26,000 m3 for algae during 2 years. This is enough to produce 130 g algal carbon in little more than 2 years assuming a constant concentration of 5 mg/m3. It is more efficient to bring 4 tons of graphite to Mars for initial steel production or consider reflecting surfaces other than polished steel.
Alternative use of covered craters to accumulate water using native perchlorates
In light of the considerable difficulties associated with installing long water pipelines to fill craters with water, we outline an elegant alternative strategy for gradually capturing water from the atmosphere using native perchlorates in the Martian sediments.
Perchlorate salts have been detected in Martian sediments and craters such as the Dale Crate and at concentrations of 0.5-1% globally. Calcium perchlorate is an extremely hygroscopic component of the Martian soil that was recently discovered to cyclically draw H2O from the Martian atmosphere into the soil by night to form saline liquid brine. By sealing the crater covers by day, when the water normally sublimates off, and then opening in-current or one way valves by night after photosynthetically formed O2 has been recovered, atmospheric water vapor can slowly be accumulated as brine liquid/ice inside of the crater at zero or minimal energetic cost.
Halophilic algae tolerate high salt concentrations and low temperatures. Due to the high concentration of CO2 in the native atmosphere the crater covering will amplify the warming effects of this greenhouse gas to prolong the duration of liquid state water needed for nitrogen and carbon fixation. By transporting more soil-derived perchlorates, possibly with crushed water ice deposits, into the covered crater, water can slowly be accumulated. Biologically formed nitrous oxide gas might further accentuate the internal greenhouse warming and thus biological rates of activity.
Perchlorates salts from inside the crater can be recovered from the liquid brine to gradually reduce the salinity of the water. This could be done using parabolic evaporation troughs periodically lifted above the briny surface. Since perchlorates are considered a human toxin, they can be removed by some microbes such as perchlorate reducing bacteria (PRBs) which use percholorates as alternative electron acceptors. Such PRBs could be introduced at a later stage to eventually render the water-filled covered craters non toxic to higher forms of life.
Soil conditioning through phototrophic primary productivity
Lichen and blue green algae have both been used as foods on Earth for hundreds of years. Spirulina is one example of a widely consumed cyanobacterium that uses sunlight to synthesize essential vitamins, antioxidants like beta-carotene and fatty acids from CO2. One major advantage of using a nitrogen fixing cyanobacterium is that they can use solar energy to convert atmospheric nitrogen gas directly into the essential amino acids that future manned missions will need to build and maintain muscle on the Red planet. This will reduce the amount of fuel spent on shuttling food supplies in. Surprisingly, some species of cyanobacteria contain 60% protein per dry gram which is more protein than beefsteak, without the high amount of deleterious cholesterol. Gaseous nitrogen makes up roughly 2.7% of Mars’ thin atmosphere and is available globally. Nitrogen gas is not the only bioavailable form of nitrogen needed to grow oxygenic phototrophs. Nitrates are an ideal fertilizer. The Curiosity rover identified bioavailable nitrates as a significant component of the sediment on Mars. Trace elements are also present in rocks and soil but may require processing.
Production of steel for structural support of Mars surface components
Steel cannot be brought to Mars as there will be at least 2.2 tons of steel necessary for structural support for 1,400 m2 perovskite solar panels. While lightweight carbon fiber modules could be used as structural support, it is possible to produce steel in situ. Steel production on Mars seems an apparent alternative to transport of construction material given the abundance of iron, nickel and titanium on Mars. However, it also requires organic carbon which is to be produced by CO2-fixing algae that grow first in enrichment tanks (transparent plastic bags) and later in covered craters. After dehydrating the algae medium, recycling and reheating it, dry algae pellets will be used as supplement for steel production. The dehydration and reheating process require additional energy which can be provided as heat using parabolic collectors. Parabolic collectors are more efficient in terms of energy capturing and easier to construct as polished steel can be used as opposed to organic Pb/I composites in perovskite solar cells. Steel is then shaped and polished to build parabolic thermal collectors to melt more ice and provide more energy until the NFR and solar panels can be fully replaced by parabolic collectors that can also produce electricity. The production of steel is limited by the amount of organic carbon available. Therefore, we recommend to explore the possibility to use methane gas as reductant and carbon source for steel production. Methane gas production is faster and requires less water resources than algae.
The Mars landers will also mine iron ores and silicates for the production of wires, solar panels and construction materials. Steel will be produced in an induction furnace using iron ores and graphite or organic biomass. Organic biomass from algae tanks will be used for steel production. This organic biomass will also be used for graphite production at a later stage of the mission. Alternative furnace concepts are possible. For example, methane can be used as reductant. Another alternative would be an electric arc furnace or sacrificial graphite electrodes. Graphite can be produced from organic carbon as follows
Organic carbon from CO2 by cold adapted algae
Organic carbon + 800ºC → C
C + SiO2 + 1,400ºC → SiC
SiC + 4,200ºC → graphite
The steel and graphite induction furnaces will be carried by the landers
Energy for initial steel production for the construction of the 170 kW solar plant (see “SHAB energy needs”) is produced by an NFR. A 40 kW reference NFR is recommended. Steel production from iron ore using electric smelting requires 900 kWh per ton of steel. That is, to produce enough structural support for solar panels for 6 people, about 2,000 kWh are necessary or about 3 days of energy production at full performance. This is based on the assumption that steel of 2 mm thickness and 10% of the perovskite area of 1,400 m2 is sufficient. To produce enough structural support for 3.5 MW (0.18 km2) perovskite solar cells needed for the comfortable return option, 280 tons of steel are required. At 50 days of steel production using the entire 210 kW (40 kW NFR + 170 kW solar perovskite life support) are anticipated. To add 1.5% carbon, 4 tons of graphite are necessary which will be carried as cargo from Earth.
Steel is necessary for parabolic heat collectors on site as well. Parabolic heat collectors are required for melting ice for algae growth. The production of steel sufficient for parabolic collectors to melt 1 billion m3 of ice is approximately 600 tons, i.e. 9 additional tons of graphite need to be shipped. To make this amount of steel on Mars another 2 years will be necessary at least. This appears to be the best trade-off between cargo transport and waiting time for a Mars mission but is still an approximation. The algal side product oxygen, also justifies this approach. Since the launch of a manned mission is not dependent on algae production, it is not counted as wait time, which would add another 4 years prior to launch. This shall only demonstrate the feasibility of in situ steel production on Mars. As alternative, the use of methane produced on Mars as carbon and electron source for steel needs to be explored as this may eliminate the need for graphite transport or carbon fiber construction materials are transported to Mars.
Possible perovskite production and reuse of lead produced by the nuclear fission reactor
Lead remnants from the 235U nuclear fission reactor aboard the landers can be used as they are a side product of the radioactive decay of contaminating 238U. There are no confirmed higher concentrations of iodine on Mars and this element needs to be brought in the form of elemental iodine, KI or NaI with the lander to produce the PbI and methyl ammonium iodide. However, since iodine can be replaced by the element chlorine for perovskite production, the initial amount iodine may not need to be replenished because chlorine is an abundant element on Mars.
Solvents required for perovskite cells can be produced in situ using methane gas and acetic acid (also a possible side product of MERs) as precursors as soon as they become available. To bridge the intermediate gap, solvents and organic reactants brought to Mars by the landers may be used. These materials are:
As synthesis of perovskite cells may still be to difficult on Mars, we recommend the transport of these components. As shown below (Surface habitat [SHAB] energy needs), only 9 kg perovskite solar panels will be required. As photo voltaic systems are constantly improved, one can expect better performance and lighter weights in future.
Devices included in this chart of the current state of the art have efficiencies that are confirmed by independent, recognized test labs (NREL, AIST, JRC-ESTI, and Fraunhofer-ISE) and are reported on a standardized basis (Source: NREL 2019)
Surface habitat (SHAB) energy needs
The average energy need per capita in the European Union was 150 GJ/year. Although this estimate is likely too high for a permanent colony on Mars we used this as reference herein. A perovskite solar panel operating at 12% efficiency can produce 14 MJ/day/m2 from Mars aphelion 8 hour solar radiation assuming 170 W/m2. That is, 240 m2 methyl ammonium lead halide perovskite solar panels are required to sustain the presence of one person on Mars. This requires 350 g mesoporous TiO2, 370 g Au per capita. The light weight of about 720 g per capita makes a transport of these components from Earth to Mars feasible (8.5 kg total). Mounting the thin solar power collector on a stable steel surface can be achieved on Mars but only if steel is produced in situ. NASA’s Human Exploration of Mars Design Reference Architecture recommends a mission of 6 explorers. That is, at about 1,400 m2 perovskite solar panels or 170 kW capacity will be required only to sustain life of one manned explorer mission. Before installation of these panels, steel will have to be produced on which they can be mounted. For the envisioned larger energy needs, 3.5 MW are necessary and for this, about 6.3 tons of perovskite may be shipped to Mars.
Yeasts such as Saccharomyces cerevisiae are, as the name suggests, used for large scale production of beer and other alcoholic beverages. Their high salt and ethanol tolerance not only makes them useful for the production of beverages, but also suitable for the production of combustion fuels at high alcohol concentrations. Besides ethanol, long-chain fusel alcohols are of high interest for biofuel production as well. Bioethanol is already mixed with gasoline and thus improves the CO2 balance of internal combustion engines. This liquid biofuel is made from either starch or lignocellulose. The production and use of bioethanol supports local economies, reduces CO2 emissions and promotes self-sufficiency. The latter is especially important for resource-depleted landlocked countries.
In order to efficiently produce ethanol and other alcohols from lignocellulose hydrolysates, yeasts must use both glucose and pentoses such as xylose and arabinose. This is because biomass is rich in both lignocellulose and thus glucose and xylose. However, this is also the main disadvantage of using Saccharomyces cerevisiae because it does not ferment xylose. Consequently, the identification of another yeast strains capable of fermenting both these sugars could solve the problem. Highly efficient yeasts can be grown in co-cultures with other yeasts capable of lignocellulose fermentation for ethanol production. Such a yeast is, for example, Wickerhamomyces anomalous.
To further improve ethanol production, bioelectric fermentation technology supporting traditional fermentation can be used. The microbial metabolism can thus be controlled electrochemically. There are many benefits of this technology. The fermentation process becomes more selective due to the application of an electrochemical potential. This, in turn, increases the efficiency of sugar utilization. In addition, the use of additives to control the redox equilibrium and the pH is minimized. Ultimately cell growth can be stimulated, further increasing alcohol production.
Such bioelectric reactors are galvanic cells. The electrodes used in such a bioelectric reactor may act as electron acceptors (anodes) or source (cathodes). Such electrochemical changes affect the metabolism and cell regulation as well as the interactions between the yeasts used. Now, a research group from Nepal (a resource-depleted landlocked country) has used new yeast strains of Saccharomyces cerevisiae and Wickerhamomyces anomalous in a bioelectric fermenter to improve ethanol production from biomass. The results were published in the journal Frontiers in Energy Research.
For their study, the researchers chose Saccharomyces cerevisiae and Wickerhamomyces anomalus as both are good ethanol producers. The latter is to be able to convert xylose to ethanol. After the researchers applied a voltage to the bioelectrical system, ethanol production doubled. Both yeasts formed a biofilm on the electrodes, making the system ideal for use as a flow-through system because the microorganisms are not washed out.
Saccharomyces cerevisiae cells in a brightfield microscopic image of 600-fold magnification (Foto: Amanda Luraschi)
The researchers speculated that the increased ethanol production was due to the better conversion of pyruvate to ethanol − the yeast’s central metabolic mechanism. The researchers attributed this to accelerated redox reactions at the anode and cathode. The applied external voltage polarized the ions present in the cytosol, thus facilitating the electron transfer from the cathode. This and the accelerated glucose oxidation probably led to increased ethanol production.
Normally, pyruvate is converted into ethanol in fermentation yeast. External voltage input can control the kinetics of glucose metabolism in Saccharomyces cerevisiae under both aerobic and anaerobic conditions. Intracellular and transplasmembrane electron transfer systems play an important role in electron transport across the cell membrane. The electron transfer system consists of cytochromes and various redox enzymes, which confer redox activity to the membrane at certain sites.
The authors also found that an increased salt concentration improved conductivity and therefore ethanol production. The increased ethanol production from lignocellulosic biomass may have been also be due to the presence of various natural compounds that promoted yeast growth. When the cellulose acetate membrane was replaced by a Nafion™ membrane, ethanol production also increased. This was perhaps due to improved transport of xylose through the Nafion™ membrane as well as the decrease of the internal resistance. A further increase of ethanol production was observed when the bioelectrical reactor was operated with fine platinum particles coated on the platinum anode and neutral red deposited on the graphite cathode.
Several yeast cultures from left to right: Saccharomyces cerevisiae, Candida utilis, Aureobasidium pullulans, Trichosporum cutaneum, Saccharomycopsis capsularis, Saccharomycopsis lipolytica, Hanseniaspora guilliermondii, Hansenula capsulata, Saccharomyces carlsbergensis, Saccharomyces rouxii, Rhodotorula rubra, Phaffia rhodozyba, Cryptococcus laurentii, Metschnikowia pulcherrima, Rhodotorula pallida
Recently, we reported on plans by Australian entrepreneurs and their government to use ammonia (NH3) to store excess wind energy. We proposed converting ammonia and CO2 from wastewater into methane gas (CH4), because it is more stable and easier to transport. The procedure follows the chemical equation:
8 NH3 + 3 CO2 → 4 N2 + 3 CH4 + 6 H2O
Now we have published a scientific article in the online magazine Frontiers in Energy Research where we show that the process is thermodynamically possible and does indeed occur. Methanogenic microbes in anaerobic digester sludge remove the hydrogen (H2) formed by electrolysis from the reaction equilibrium. As a result, the redox potentials of the oxidative (N2/NH3) and the reductive (CO2/CH4) half-reactions come so close that the process becomes spontaneous. It requires a catalyst in the form of wastewater microbes.
Pourbaix diagram of ammonium oxidation, hydrogen formation and CO2 reduction. At pH 7 and higher, the oxidation of ammonium coupled to methanogenesis becomes thermodynamically possible.
To prove our idea, we first searched for the right microbes that could carry out ammonia oxidation. For our experiments in microbial electrolysis cells we used microorganisms from sediments of the Atlantic Ocean off Namibia as starter cultures. Marine sediments are particularly suitable because they are relatively rich in ammonia, free from oxygen (O2) and contain less organic carbon than other ammonia-rich environments. Excluding oxygen is important because it used by ammonia-oxidizing microbes in a process called nitrification:
2 NH3+ + 3 O2 → 2 NO2− + 2 H+ + 2 H2O
Nitrification would have caused an electrochemical short circuit, as the electrons are transferred from the ammonia directly to the oxygen. This would have bypassed the anode (the positive electron accepting electrode) and stored the energy of the ammonia in the water − where it is useless. This is because, anodic water oxidation consumes much more energy than the oxidation of ammonia. In addition, precious metals are often necessary for water oxidation. Without producing oxygen at the anode, we were able to show that the oxidation of ammonium (the dissolved form of ammonia) is coupled to the production of hydrogen.
Oxidation of ammonium to nitrogen gas is coupled to hydrogen production in microbial electrolysis reactors. The applied potentials are +550 mV to +150 mV
It was important that the electrochemical potential at the anode was more negative than the +820 mV required for water oxidation. For this purpose, we used a potentiostat that kept the electrochemical potential constant between +550 mV and +150 mV. At all these potentials, N2 was produced at the anode and H2 at the cathode. Since the only source of electrons in the anode compartment was ammonium, the electrons for hydrogen production could come only from the ammonium oxidation. In addition, ammonium was also the only nitrogen source for the production of N2. As a result, the processes would be coupled.
In the next step, we wanted to show that this process also has a useful application. Nitrogen compounds are often found in wastewater. These compounds consist predominantly of ammonium. Among them are also drugs and their degradation products. At the same time, 1-2% of the energy produced worldwide is consumed in the Haber-Bosch process. In the Haber-Bosch process N2 is extracted from the air to produce nitrogen fertilizer. Another 3% of our energy is then used to remove the same nitrogen from our wastewater. This senseless waste of energy emits 5% of our greenhouse gases. In contrast, wastewater treatment plants could be net energy generators. In fact, a small part of the energy of wastewater has been recovered as biogas for more than a century. During biogas production, organic material from anaerobic digester sludge is decomposed by microbial communities and converted into methane:
The reaction produces CO2 and methane at a ratio of 1:1. Unfortunately, the CO2 in the biogas makes it almost worthless. As a result, biogas is often flared off, especially in places where natural gas is cheap. The removal of CO2 would greatly enhance the product and can be achieved using CO2 scrubbers. Even more reduced carbon sources can shift the ratio of CO2 to CH4. Nevertheless, CO2 would remain in biogas. Adding hydrogen to anaerobic digesters solves this problem technically. The process is called biogas upgrading. Hydrogen could be produced by electrolysis:
2 H2O → 2 H2 + O2; ∆G°’ = +237 kJ/mol (H2)
Electrolysis of water, however, is expensive and requires higher energy input. The reason is that the electrolysis of water takes place at a relatively high voltage of 1.23 V. One way to get around this is to replace the water by ammonium:
2 NH4+ → N2 + 2 H+ + 3 H2; ∆G°’ = +40 kJ/mol (H2)
With ammonium, the reaction takes place at only 136 mV, which saves the respective amount of energy. Thus, and with suitable catalysts, ammonium could serve as a reducing agent for hydrogen production. Microorganisms in the wastewater could be such catalysts. Moreover, without oxygen, methanogens become active in the wastewater and consume the produced hydrogen:
The methanogenic reaction keeps the hydrogen concentration so low (usually below 10 Pa) that the ammonium oxidation proceeds spontaneously, i.e. with energy gain:
The low energy gain is due to the small potential difference of ΔEh = +33 mV of CO2 reduction compared to the ammonium oxidation (see Pourbaix diagram above). The energy captured is barely sufficient for ADP phosphorylation (ΔG°’ = +31 kJ/mol). In addition, the nitrogen bond energy is innately high, which requires strong oxidants such as O2 (nitrification) or nitrite (anammox) to break them.
Instead of strong oxidizing agents, an anode may provide the activation energy for the ammonium oxidation, for example when poised at +500 mV. However, such positive redox potentials do not occur naturally in anaerobic environments. Therefore, we tested whether the ammonium oxidation can be coupled to the hydrogenotrophic methanogenesis by offering a positive electrode potential without O2. Indeed, we demonstrated this in our article and have filed a patent application. With our method one could, for example, profitably remove ammonia from industrial wastewater. It is also suitable for energy storage when e.g. Ammonia synthesized using excess wind energy.
Since Professor Potter’s discovery of the ability of microbes to turn organic molecules into electricity using microbial fuel cells (MFC) more than a century ago (Potter MC, 1911, Proc Roy Soc Lond Ser B 84:260–276), much research was done to improve the performance. Unfortunately, this did not not produce an economically viable technology. MFCs never made it out of the professors’ class rooms. This may change now that we have advanced nanomaterials available.
The testing of nanomaterials in bio-electrical systems has experienced a Cambrian explosion. The focus usually was on electrodes, membranes, and in the electrolyte with infinite possibilities to find high performing composites. The benefits of such materials include a large surface area, cost savings, and scalability. All are required to successfully commercialize bio-electrical systems. The large-scale commercial application could be wastewater treatment. In our recently published literature survey we discovered that there is no common benchmark for performance, as it is usual in photovoltaics or for batteries. To normalize our findings, we used dollar per peak power capacity as ($/Wp) as it is standard in photovoltaics. The median cost for air cathodes of MFCs is $4,700 /Wp ($2,800 /m²). Platinum on carbon (Pt/C) and carbon nanofibers are the best performing materials with $500 /Wp (Pt/C $2,800 /m²; nanofibers $2,000 /m²).
We found that carbon-based nanomaterials often deliver performance comparable to Pt/C. While MFCs are still far away from being profitable, microbial electrolysis cells already are. With these new carbon-based nanomaterials, MFCs however, are moving closer to become an economic reality. Graphene and carbon nanotubes are promising materials when they are combined with minerals such as manganese or iron oxides. However, the price of graphene is still too expensive to let MFCs become an economic reality in wastewater treatment. The costs of microbial electrolysis, however, are already so low that it is a serious alternative to traditional wastewater treatment as we show in the featured image above. For high strength wastewater, a treatment plant can in fact turn into a power plant with excess power being offered to surrounding neighborhoods. Reducing the costs of microbial electrolysis is accomplished by using a combination of cheap steel and graphite.
Relationship between MEC reactor capacity and total electrode cost including anode and cathode. Errors are standard deviations of four different tubular reactor designs. Anodes are graphite granules and cathodes are steel pipes
Graphite, in turn, is the precursor of graphene, a promising material for MFC electrodes. When graphite flakes are reduced to a few graphene layers, some of the most technologically important properties of the material are greatly improved. These include the overall surface and the elasticity. Graphene is therefore a very thin graphite. Many manufacturers of graphene use this to sell a material that is really just cheap graphite. In the journal Advanced MaterialsKauling and colleagues published a systematic study of graphene from sixty manufacturers and find that many high-priced graphene products consist mainly of graphite powder. The study found that less than 10% of the material in most products was graphene. None of the tested products contained more than 50% graphene. Many were heavily contaminated, most likely with chemicals used in the production process. This can often lead to a material having catalytic properties which would not have been observed without contamination, as reported by Wang and Pumera.
There are many methods of producing graphene. One of the simplest is the deposition on a metallic surface, as we describe it in our latest publication:
Single-layer graphene (SLG) and multilayer graphene (MLG) are synthesized by chemical vapor deposition (CVD) from a carbon precursor on catalytic metal surfaces. In a surface-mediated CVD process, the carbon precursor, e.g. Isopropyl alcohol (IPA) is decomposed on the metal surface, e.g. Cu or Ni. In order to control the number of graphene layers formed, the solubility of the carbon precursor on the metal catalyst surface must be taken into account. Due to the low solubility of the precursor in Cu, SLG can be formed. It is difficult to grow SLG on the surface of a metal with a high affinity for the precursor.
Protocol: The protocol is a cheap, safe and simple method for the synthesis of MLG films by CVD in 30-45 minutes in a chemistry lab. A nickel foil is submersed in acetic acid for etching and then transferred to an airtight quartz tube. The same protects the system from ambient oxygen and water vapor. Nitrogen gas is bubbled through the IPA and the resulting IPA saturated gas is passed through the closed system. The exhaust gases are washed in a beaker with a water or a gas wash bottle. The stream is purged for 5 minutes at a rate of about 50 cc/min. As soon as the flame reaches a Meker burner 575-625 °C, it is positioned under the nickel foil, so that sufficient energy for the formation of graphene is available. The flame is extinguished after 5-10 minutes to stop the reaction and to cool the system for 5 minutes. The graphene-coated Ni foil is obtained.
But how thin must graphite flakes be to behave as graphene? A common idea supported by the International Organization for Standardization (ISO) is that flakes with more than ten graphene layers consist essentially of graphite. Thermodynamics say that each atomic layer in a flake with ten or fewer layers at room temperature behaves as a single graphene crystal. In addition, the stiffness of the graphite flakes increases with the layer thickness, which means that thin graphene flakes are orders of magnitude more elastic than thicker graphite flakes.
Unfortunately, to actually use graphene in bioelectric reactors, you still have to make it yourself. The ingredients can be found in our DIY Shop.
