Powering an engine with hydrogen derived from formic acid

[William Gaatjes]

This seems promising. But formic acid is highly corrosive i read.

The whole idea is to run a "gasoline" engine on hydrogen.
But the problem is to store hydrogen in enough quantity that it becomes useful.
That means high pressure hydrogen storage.

To make the whole idea of driving on hydrogen safer, this principle converts formic acid into hydrogen. There is just formic acid in storage.
But the whole idea makes me worry. Driving around with a corrosive acid.
Storing it is not such a problem, i am sure there exists plastics that do not get affected by formic acid. I have seen plastic containers that can hold very corrosive substances for years when i visited a company that produced chemicals. Everything metal is affected by those chemicals , but the plastic is not. I assume, that is not an issue. And there are automobiles out there , with a plastic gasoline tank as well.

But as always, there is a negative side.
Does anybody know ?

How is the chemical reaction from formic acid to hydrogen ?
Is it really that clean ?

And when compared how much energy is in one gram of formic acid compared to one gram of gasoline, what is the efficiency when compared to gasoline ?

For background information (in English):

http://www.teamfast.nl/

http://www.betterworldsolutions.eu/car-driving-on-formic-acid-high-potential-new-technology/

Students from the Eindhoven University of Technology have developed a car prototype that works on Formic Acid. To produce the formic acid, CO2 is needed to attach the hydrogen to the CO2. In the car, formic acid is converted to Hydrogen and CO2. For this conversion, the catalyst’s function is to fasten this reaction.

In the car, the hydrogen is used to generate electricity for the motor. The CO2 is released to the air again, like where it had been extracted.

There are some points which need more research. Corrosion is one of them.
It is STILL uncertain whether components such as the catalyst, will be resistant to the acid in the long term.
Another point of attention is that formic has a pH of 4.5. For methanol the pH is 12.5. Methanol can do the same, while the fuel tank is much smaller. However, methanol is flammable and formic acid is not.

not flammable

not explosive

and at room temperature, it is liquid
so it doesn’t need tank transportation under extremely high pressure

in addition, the energy density is high.
A car with a tank of 100 liters can drive approximately 500 km; the range is much longer than battery cars and about as far as hydrogen cars.

moreover it has a high ignition point; higher than diesel fuel

http://phys.org/news/2016-01-dutch-student-team-world-car.html




https://en.wikipedia.org/wiki/Formic_acid

 

[William Gaatjes]

I will just add this.
This seems very promising.

First car to run on formic acid

In 2017 Team FAST wants to have built the world's first car powered by formic acid. They will do that by converting an existing hydrogen-powered car. Today the team presents the proof on a small scale: a scale model, a meter in size, which is able to drive on formic acid. Before the year is out they hope to demonstrate the concept in a bus.

Team FAST is a multidisciplinary team of 20 students. Their idea for a formic acid powered car won them one of the Eindhoven BRAINS awards for sustainability last year as well as a grant of 50,000 euros in the Dutch STW technology foundation's Open Mind competition.


Read more at: http://phys.org/news/2016-01-dutch-student-team-world-car.html#jCp

http://phys.org/news/2012-08-hydrogenation-carbon-dioxide-pure-formic.html

Continuous hydrogenation of carbon dioxide to pure formic acid in supercritical CO2

(Phys.org) -- To reduce fossil fuel consumption while simultaneously improving the carbon footprint of fuels and chemical products, the use of carbon dioxide as a carbon source could be an attractive option. In the journal Angewandte Chemie, German researchers have now introduced a method by which carbon dioxide can be catalytically hydrogenated to make formic acid. In this process, carbon dioxide is not only a starting material; it also acts—in a supercritical state—as the solvent for separation of the product. This integrated approach makes it possible to directly obtain free formic acid as the product in a single step for the first time.

The hydrogenation of CO2 to formic acid (HCO2H) is a subject of intensive research because it offers direct access to chemical products based on waste products from the use of fossil fuels for energy. Formic acid is an important product in the chemical industry and has many applications, including agriculture, food technology, and the leather industry. It is also being contemplated as a potential hydrogen-storage material: vehicles powered by fuel cells could fill up with formic acid, from which the hydrogen could then be produced catalytically.

Homogeneous catalysts for the production of formic acid from CO2 have been investigated since the mid 1970s. The trouble with this process is that it involves an equilibrium reaction for which the equilibrium heavily favors the reactants. In order to suppress the constantly occurring back-reaction, the formic acid must be removed—in the form of a salt, adduct, or derivative—to take it out of the equilibrium. To obtain the desired free formic acid in the end, additional separation steps are thus required to separate the adducts from the catalyst and finally to release and isolate the formic acid.

A team led by Walter Leitner at the RWTH Aachen University has now developed a new concept that can be used to produce pure formic acid in a continuous process. The reaction and separation steps are integrated in a single processing unit.

Their trick is to use a two-phase reaction system that employs supercritical CO2 as the mobile phase and a liquid salt—an ionic liquid—as the stationary phase. The catalyst and the base used to stabilize the formic acid are both dissolved in the ionic liquid, which holds them both in the reactor. The CO2 flows through the reactor at pressures and temperatures above the critical values (74 bar, 31 °C) and selectively removes the formic acid from the mixture. The dual role played by CO2 as both reactant and extractive phase has significant advantages: The product is continuously extracted and flushed from the reactor, which causes the equilibrium to readjust constantly. Once out of the reactor, the free formic acid can be obtained with high purity by decompression or washing. Ionic liquids do not dissolve in supercritical CO2, nor do the catalyst and base, so these do not contaminate the product. The process can run continuously. In laboratory experiments, stable operation was demonstrated for over 200 hours.

“Our results with formic acid demonstrate that the systematic implementation of modern solvent techniques in continuous reactor equipment makes it possible to perform conversions that cannot be achieved under conventional conditions,” says Leitner. “Naturally we can’t ‘defeat’ thermodynamics in this way—but there are many possibilities for the integration of reactions and materials separation that may open new routes for more efficient and sustainable processes.”


Read more at: http://phys.org/news/2012-08-hydrogenation-carbon-dioxide-pure-formic.html#jCp

http://phys.org/news/2010-12-formic-acid.html
Video inside.

Formic acid in the engine

(PhysOrg.com) -- Do ants hold the key to the fuel of the future? Formic acid provides more efficient and safer storage of hydrogen. It is an ideal way to store energy from renewable sources or to power 21st century cars.
Hydrogen is often referred to as the future replacement for fossil fuels. Despite being environmentally-friendly and efficient, it nevertheless has many drawbacks. Because it is extremely flammable, it must be stored in bulky pressurized cylinders. Scientists from the EPFL and their colleagues at the Leibniz-Institut für Katalyse have found a way around these obstacles. Once converted to formic acid, hydrogen can be stored easily and safely. This is an ideal solution for storing energy from renewable sources like solar or wind power, or to power the cars of tomorrow.
Hydrogen is easy to produce from electrical energy. With a catalyst and the CO2 present in the atmosphere, scientists have been able to convert it to formic acid. Rather than a heavy cast iron cylinder filled with pressurized hydrogen, they obtain a non-flammable substance that is liquid at room temperature.
In November 2010, EPFL laboratories produced the opposite reaction. Through a catalytic process, the formic acid reverts to CO2 and hydrogen, which can then be converted into electricity. A compact working prototype producing 2 kilowatts of power has been developed, and two companies have purchased a license to develop this technology: Granit (Switzerland) and Tekion (Canada).

Storing Renewable Energy

“Imagine for example that you have solar panels on your roof,” says Gabor Laurenczy, professor at the Laboratory of Organometallic and Medicinal Chemistry and Head of the Group of Catalysis for Energy and Environment.“In bad weather or at night, your formic acid battery will release the excess energy stored while the sun was shining.” In such a configuration, the method can restitute more than 60% of the original electrical energy.
This solution is extremely safe. The formic acid continuously releases very small amounts of hydrogen, “just what you need at the time for your energy consumption,” says the researcher.
Another advantage over conventional storage is that the method can store almost twice as much energy at equal volume. One liter of formic acid contains more than 53 grams of hydrogen, compared to just 28 grams for the same volume of pure hydrogen pressurized to 350 bars.
Finally, the researchers have developed a catalytic process using iron, which is readily available and inexpensive compared to “noble” metals such as platinum or ruthenium. As with all catalysts, no material is degraded during the process.

Formic acid at the pump

It is probably in the automotive field that the invention has the greatest potential. Currently, the prototypes produced by certain carmakers store hydrogen in conventional form, which entails problems such as risk of explosion, large volume pressurized tanks, difficulties in filling the tank quickly, etc.
The vehicles of the 21st century may run on formic acid. This solution allows for safer, more compact hydrogen storage as well as easier filling at the pump – formic acid is liquid at room temperature. “Technically, it is quite feasible. In fact, a number of major automobile manufacturers contacted us in 2008, when oil prices reached record highs,” says Gabor Laurenczy. “In my opinion, the only obstacle is cost.” It will be several years before drivers can pull up to any anthill and fill their tanks.

Read more at: http://phys.org/news/2010-12-formic-acid.html#jCp

 

[tynopik]

if we're going to play with dangerous chemicals, wouldn't it be easier to just use ammonia (NH3)?

formic acid: 5.2 MJ/kg
ammonia: 22.5 MJ/kg

 

[William Gaatjes]

if we're going to play with dangerous chemicals, wouldn't it be easier to just use ammonia (NH3)?

It is not that dangerous. It is just corrosive :hmm:. Only the storage compartment holding the formic acid and the part that does the conversion needs to be protected against corrosion.
And the discovery of creating formic acid by making use of CO2 from the air seems to be a good idea. It is sort of carbon neutral. Nothing we can do really is, but it is good to approach it.
In creating Ammonia there is no CO2 to be used, i believe. But then again, i have no chemical background.

 

[MagnusTheBrewer]

Can someone please tell me what "super critical CO2" is?

 

[Brainonska511]

Can someone please tell me what "super critical CO2" is?

Supercritical substances are when you have it at a temperature above its critical point. At the critical point, the transition between liquid and gas ceases to exist and you have neither a liquid nor a gas, but it has properties of both phases.

https://en.wikipedia.org/wiki/Supercritical_carbon_dioxide

 

[MagnusTheBrewer]

Thank you. So, in this case, the CO2 has to start out frozen? I thought it was extracted from the air? Sorry if I missed something obvious.

 

[William Gaatjes]

Thank you. So, in this case, the CO2 has to start out frozen? I thought it was extracted from the air? Sorry if I missed something obvious.

That is an interesting question. I too would like to now how the CO2 is extracted from air ?
And how do they get the CO2 in such a state ?

I know the biggest advantage is that it can be done in a factory, so it is stationary. Which makes it easier to create large structures that do not have to be moved. And it is easier to prevent polluting materials to just enter the air. Everything bulky can just be set up. Cleaning up, filters and waste collection/ processing.

 

[Brainonska511]

Thank you. So, in this case, the CO2 has to start out frozen? I thought it was extracted from the air? Sorry if I missed something obvious.

Admittedly, I haven't read any of the linked articles here, but I don't see why you'd have to start with the CO2 frozen to generate supercritical CO2. You could always just compress and heat CO2 gas to make supercritical CO2.

 

[William Gaatjes]

Admittedly, I haven't read any of the linked articles here, but I don't see why you'd have to start with the CO2 frozen to generate supercritical CO2. You could always just compress and heat CO2 gas to make supercritical CO2.

Woops. Now that you mention that, i recall reading that they use high pressures and medium temperatures.
It is partially explained above.

 

[Brainonska511]

That is an interesting question. I too would like to now how the CO2 is extracted from air ?

https://en.wikipedia.org/wiki/Carbon_dioxide#Isolation_and_production

Seems like most CO2 purification is achieved through other industrial processes and not from distillation from air.

 

[William Gaatjes]

https://en.wikipedia.org/wiki/Carbon_dioxide#Isolation_and_production

Seems like most CO2 purification is achieved through other industrial processes and not from distillation from air.

Aha, we can make use of waste processing to capture CO2.

Now i remember reading about a underground landfill near Amsterdam , the Netherlands called Diemerzeedijk. It was in the past used to dump waste, now it is contained and it is a park. After cleaning up by use of soil remediation a pipe and pump system was set up that constantly collects mainly the water and some gas from the underground landfill. Also, non stop measurements are being performed to track any nasty problem ahead before it becomes a serious problem.

EDIT:
They do check for gas, but i got it wrong, they filter the underground water that is heavily contaminated with heavy metals, PAKS , PCB and dioxines. They pump out the groundwater from the isolated underground land fill, filter it and after it is cleaned it is being pumped in the sewer.
What they did, is put all the waste inside a huge box with a circumference of 5km and it is about 26 meter deep.
A shoebox upside down on a clay layer. And in that shoebox, the groundwater is pumped out and filtered. To prevent it from contaminating the surrounding soil.


As intermezzo for those interested :
It is in Dutch, so i used google translate. Be a bit forgiving for the rough translation. But it has a lot of pictures.

https://translate.google.com/transl...ompen-bij-de-diemerzeedijk&edit-text=&act=url

 

[Ken g6]

It is not that dangerous. It is just corrosive :hmm:.

Heat and especially acids cause formic acid to decompose to carbon monoxide (CO) and water (dehydration).

So, produces carbon monoxide if heated, but not "that dangerous"?

 

[William Gaatjes]

So, produces carbon monoxide if heated, but not "that dangerous"?

Well, do not heat it. Or inhale the fumes. Assuming it will be a closed system. The formic acid tank will need a venting pressure system since it slowly seems to decompose in CO and water. But the release of CO will probably be a few orders in magnitude less than a gasoline burning car. I say a non issue.
Nothing is perfect. But trying to get there is a good thing.
Everything in life can be seen as an asymptote.

 

[Red Squirrel]

The issue is, how easy is it to make or get formic acid? If it's something that's complex like fossil fuel it will just end up in the same boat where there is a single world power that controls the price. But if it's a clean reaction and that there is no dangerous byproduct, then it's a step in the right direction.

 

[William Gaatjes]

The issue is, how easy is it to make or get formic acid? If it's something that's complex like fossil fuel it will just end up in the same boat where there is a single world power that controls the price. But if it's a clean reaction and that there is no dangerous byproduct, then it's a step in the right direction.

According to the wiki, it is a byproduct of a lot of industrial processes. I too hope that the process to create is quite clean. It seems to be with what i have read so far.

When comparing with bio ethanol.
It sure beats ethanol created from large crop fields that could be used for food instead of ethanol creation. Would mean less rain forests destroyed.
May have lower energy per gram but it could be cleaner in the end.
Perhaps in the future this could be possible :

Formic acid in tank.
Formic acid to hydrogen conversion.
Fuel cell performs hydrogen to electricity, byproduct water.
Electric motors.

But for that to work, all the efficiency losses must be less than with a car as stated in the first post.

There will be enough work for the researchers. But that oil is coming to an end anyway. The ground work may as well be done now.

 

[Red Squirrel]

Or if fuel cell is dense enough maybe go straight to that, if everyone has solar panels and wind turbines and other renewable energy and plugs in every night it could charge the fuel cells directly.

Only thing, fuel cells are basically water right? Not sure how well they would do in a car as it would freeze.