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Ammonia energy storage #2

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:

H3C−COO + H+ + H2O → CH4 + HCO3 + H+; ∆G°’ = −31 kJ/mol (CH4)

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:

4 H2 + HCO3 + H+ → CH4 + 3 H2O; ∆G°’ = –34 kJ/mol (H2)

The methanogenic reaction keeps the hydrogen concentration so low (usually below 10 Pa) that the ammonium oxidation proceeds spontaneously, i.e. with energy gain:

8 NH4+ + 3 HCO3 → 4 N2 + 3 CH4 + 5 H+ + 9 H2O; ∆G°’ = −30 kJ/mol (CH4)

This is exactly the reaction described above. Bioelectrical methanogens grow at cathodes and belong to the genus Methanobacterium. Members of this genus thrive at low H2 concentrations.

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 phosphorylationG°’ = +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.

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An inexpensive scalable multi-channel potentiostat

As our preferred reader, you know already what we work on Power-to-Gas to combat Global Warming. We think that giving CO2 a value will incentivize its recycling and recycling it into fuel turns it into a commodity that everyone needs. While the price of CO2 from air is still too high to convert it into combustion fuel, working on the other end (the CO2 conversion) will help to accommodate such high prices. We have now published an research paper that shows how how to reduce the costs of electronic equipment needed for CO2 conversion. For Power-to-Gas as well es for electrosynthesis of liquid fuels, it is necessary to poise an electrochemical potential. So far, only electronic potentiostats could do that. We have developed a software solution that can control cheap off-the-shelf hardware to accomplish the same goal. Since the software controls µA as well as MA, it is freely scalable. By stacking cheap power supplies, it can also run unlimited channels.

Frontcell© potentiostat setup with two channels. From left to right: digital multimeter (in the back), relay board (in front), two H-type electrolysis cells, power supply, control computer.

We tested the software at a typical experimental Power-to-Gas setup at −800 mV and found that the recorded potential was stable over 10 days. The small electrochemical cells could also be replaced by a larger 7 liter reactor treating real wastewater. The potential was stable as well.

The potential of −800 mV controlled by the Frontcell© potentiostat was stable for 200 ml electrolysis cells (left) as well as for a larger 7 l reactor (right).

As instrument control of mass products also makes the chemical processes involved cheap, microbial electrolysis of wastewater becomes economically feasible. Removal of wastewater organics usually occurs at positive electrochemical potentials. Indeed, the software also stabilizes such potentials at +300 mV.

The Frontcell© potentiostat stabilized a 200 ml electrolysis cells at +300 mV for ten days.

The potentiostat is currently available as command line version. We are currently accepting pre-orders at a 50% discount for the commercial version that comes with a graphical user interface and remote control using an internet browser.

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Fuel Cells Have the Potential to Become the Best Green Energy Alternative to Fossil Fuels

Global warming is – as the name already suggests – a global concern. It causes problems such as sea level rise, more frequent and more severe strms, and longer droughts. Thus, it global warming concerns all of us. To best fight global warming, adopting green energy in your life is the best viable solution.

Green energy is getting more attention today. It helps to reduce our carbon footprint and thus curbing the global warming. Increasing carbon footprint is the main cause for rising temperatures. Moreover, investing in green energy is also a business case generating steady revenue stream without marginal costs. Hence, many governments promote the use of green energy by providing subsidies and teaching people its benefits in their life.

There are many ways green energy is produced, for example, solar energy, wind energy, the energy produced through bio-waste. Fuel cells are a major breakthrough in this regard. They have impacted the production green energy in many ways. They are also convenient to use. As their fuel (hydrogen, methane …) is produced by using electrical energy, they can use a wide range of green sources to produce energy.

What Are Fuel Cells?

A fuel cells is a device that converts chemical energy into electrical energy. The process combines hydrogen and oxygen to produce water& electricity as main products. Fuel cells are somewhat similar batteries. The main difference is that a fuel is supplied without a charge-discharge cycle. Like batteries, fuel cells are portable and can be used with a variety of fuels like ethanol, methanol, methane, and more.

There are different types of fuel cells. But the most popular ones are hydrogen fuel cells that provide a wide range with only some of advantages as follows:

  • The cells are more efficient than conventional methods used to produce energy.
  • They are quiet – unlike, for example combustion engines or turbines
  • Fuel cells eliminate pollution by using hydrogen instead of burning of fossil fuels.
  • Fuel cells have a longer lifespan than batteries because fresh fuel is supplied constantly
  • They use chemical fuels that can be recycled or produced using renewable energy which makes them environmentally friendly.
  • Hydrogen fuel cells are grid-independent and can be used anywhere.

How Do Fuel Cells Work?

A fuel cell produces power by transforming chemical energy into electrical energy in reduction-oxidation processes, much like batteries do. However, unlike batteries, they produce electricity from external supplies of fuel to the anode and oxidants to the cathode. Fuel cells are capable of producing energy as long as the fuel required to produce energy is supplied. Main components of fuel cells are electrolytes that allow for ion exchange. They aid the electro chemical reaction.

Hydrogen, ethanol, methanol, and methane are used as a source of energy. Methane, which is extracted from the subsurface, can be transformed into hydrogen rich stream. With an abundance of the hydrogen in nature, fuel cells seem to be the most viable technology that helps to produce green energy at large scale and at the most affordable cost.

Fuel cells are all set to become the most reliable source of green energy in the near future. They are fuel efficient, so businesses can make the best use of them. At Frontis Energy, we offer a unique selection that helps you build and improve your own fuel cells – be it for research and development or for production.

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How do the fuel cells work as an effective renewable power?

Fuel cells are the devices that convert chemical energy directly into electrical energy. The process combines hydrogen and oxygen produce water& electricity as main products. Fuel cells are similar to batteries in that they produce electricity but also different in that a fuel is supplied without a charge-discharge cycle. Like batteries, they are portable and developed by technological experts. The cells can be used with a variety of fuels like ethanol, methanol, methane, and more.

Here are the advantages of hydrogen fuel cells –

  1. The cells are efficient when compared to the conventional forms of producing energy.
  2. Hydrogen fuel cells operate silently.
  3. Fuel cells eliminate pollution by switching from burning of fossil fuels to hydrogen.
  4. Fuel cells last longer than batteries because they use chemical fuels to produce energy.
  5. Hydrogen fuel cells are grid-independent and can be used anywhere.

Components of Fuel Cells. A fuel cell converts chemical energy into electrical energy, much like a battery. But unlike batteries, they produce electricity from external supplies of fuels to the anode and oxidants to the cathode. Fuel cells can operate virtually continuously as long as the necessary fuel is supplied. Electrolytes are the major components of the fuel cells and keep that allow ion exchange. Fuel cells also have electrodes that are catalysts of the electrical chemical reaction.

Fuel for Fuel Cells. Fuel cells can operate using a variety of fuels like hydrogen, ethanol, methanol, and methane. Fossil fuels like methane are extracted from underground and converted into a hydrogen rich stream. There is also a huge abundant amount of hydrogen in water which can be used for the hydrogen power supply .For higher voltages, fuel cells can be stacked. Fuel cells can power anything from microchips to buses, boats, and buildings.

Fuel Cell Efficiency. The fuel cells are much more efficient than conventional power generation. This is because conventional power is generated be converting chemical energy into heat, mechanical energy and lastly into electrical energy. Fuel cells are converting energy directly into electrical energy and are much more efficient.

Fuels cells are a promising technology and already a source of electricity for buildings and vehicles. The devices operate best with pure hydrogen. In contrast, fossil fuel reserves are in limited and the energy future of the world needs to include several renewable alternatives to our declining resources. Hydrogen is the most abundant element present in the universe and serves as the fuel for nuclear fusion in the sun. Due to this abundance, hydrogen fuel cells are the best green energy source.

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You Can Have the Pie and Eat It

In Paris, humanity has set itself the goal of limiting global warming to 1.5 °C. Most people believe that this will be accompanied by significant sacrifice of quality of life. That is one reason why climate protection is simply rejected by many people, even to the point of outright denial. At Frontis Energy, we think we can protect the climate and live better. The latest study published in Nature Energy by a research group around Arnulf Grubler of the International Institute for Applied Systems Analysis in Laxenburg, Austria, has now shown that we have good reasons.

The team used computer models to explore the potential of technological trends to reduce energy consumption. Among other things, the researchers said that the use of shared car services will increase and that fossil fuels will give way to solar energy and other forms of renewable energy. Their results show that global energy consumption would decrease by about 40% regardless of population, income, and economic growth. Air pollution and demand for biofuels would also decrease, which would improve health and food supplies.

In contrast to many previous assessments, the group’s findings suggest that humans can limit the temperature rise to 1.5 °C above preindustrial levels without resorting to drastic strategies to extract CO2 from the atmosphere later in the century.

Now, one can argue whether shared car services do not cut quality of life. Nevertheless, we think that individual mobility can be maintained while protecting our climate. CO2 recovery for the production of fuels (CO2 recycling that is) is such a possibility. The Power-to-Gas technology is the most advanced version of CO2 recycling and should certainly be considered in future studies. An example of such an assessment of the power-to-gas technology was published by a Swiss research group headed by Frédéric Meylan, who found that the carbon footprint can be neutralized with conventional technology after just a few cycles.

(Picture: Pieter Bruegel the Elder, The Land of Cockaigne, Wikipedia)

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Mapping Waste-to-Energy

Most readers of our blog know that waste can be easily converted into energy, such as in biogas plants. Biogas, biohydrogen, and biodiesel are biofuels because they are biologically produced by microorganisms or plants. Biofuel facilities are found worldwide. However, nobody knows exactly where these biofuel plants are located and where they can be operated most economically. This knowledge gap hampers market access for biofuel producers.

At least for the United States − the largest market for biofuels − there is now a map. A research team from the Pacific Northwest National Laboratory (PNNL) and the National Renewable Energy Laboratory (NREL) published a detailed analysis of the potential for waste-to-energy in the US in the journal Renewable and Sustainable Energy Reviews.

The group focused on liquid biofuels that can be recovered from sewage sludge using the Fischer-Tropsch process. The industrial process was originally developed in Nazi Germany for coal liquefaction, but can also be used to liquefy other organic materials, such as biomass. The resulting oil is similar to petroleum, but contains small amounts of oxygen and water. A side effect is that nutrients, such as phosphate can be recovered.

The research group coupled the best available information on these organic wastes from their database with computer models to estimate the quantities and the best geographical distribution of the potential production of liquid biofuel. The results suggest that the United States could produce more than 20 billion liters of liquid biofuel per year.

The group also found that the potential for liquid biofuel from sewage sludge from public wastewater treatment plants is 4 billion liters per year. This resource was found to be widespread throughout the country − with a high density of sites on the east cost, as well as in the largest cities. Animal manure has a potential for 10 billion liters of liquid biofuel per year. Especially in the Midwest are the largest untapped resources.

The potential for liquid biofuel from food waste also follows the population density. For metropolitan areas such as Los Angeles, Seattle, Las Vegas, New York, etc., the researchers estimate that such waste could produce more than 3 billion liters per year. However, food leftovers also had the lowest conversion efficiency. This is also the biggest criticism of the Fischer-Tropsch process. Plants producing significant quantities of liquid fuel are significantly larger than conventional refineries, consume a lot of energy and produce more CO2 than they save.

Better processes for biomass liquefaction and more efficient use of biomass still remain a challenge for industry and science.

(Photo: Wikipedia)

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The Photosynthetic CO2 Race − Plants vs. Algae

Algae store CO2 but also release it. Some of us may know that. However, so far it was unknown that algae may release additional CO2 due to global warming. That’s what researcher Chao Song and his colleagues of the University of Georgia in Athens, GA, found out.

As they published in the journal Nature Geoscience, the metabolism of algae and other microbes is accelerated by higher water temperatures in large streams. This could lead to some rivers releasing more CO2 than they do now. This could, in turn, further accelerate global warming. Although photosynthesis in algae would accelerate, plants along the river banks would be even faster. Decomposition of the plant material would immediately release the so fixed CO2. With extra nutrients from plants, competing microorganisms would overgrow the river algae or the algae would degrade the plant material themselves.

To calculate the CO2 net effect, scientists monitored temperature, dissolved oxygen, and other parameters in 70 rivers worldwide. Then they used their data for computer models. These models suggest that over time, accelerated photosynthesis in some rivers may not keep pace with plant growth. This net increase of 24% of the CO2 released from rivers could mean an additional global temperature increase of 1 °C.

However, the computer model still lacks some data. For example, the sedimentation rates are not taken into account. In addition, not all banks grow plants. Many rivers pass only sparsely vegetated land. As always, more research is needed to get better answers.

(Photo: Wikipedia)