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Hydrogen Dreams or are they ?

There is no doubt that Hydrogen grabs most headlines in clean energy promotion , seems all so simple the fuel cell can work with H2 gas and air and produce a decent amount of electrical energy .Things start getting a bit different for trying to move heavy loads or where large amounts of power are needed as what is termed the energy density starts to become important , Diesel has a very high energy density and liquid fuels in general give battery/fuel cells a good run for the money in power terms. 

Things are changing , but fuel cells remain at around 60% efficient and bit more for the very hot solid oxide ones.

There is also the development of Hydrogen to be blended in natural gas mixtures for use in Gas turbines at around 20% by volume which has been successful and now the 100% hydrogen gas turbine is being developed , given gas turbines have recently broken the barrier for heat engines with 64% efficiency ,then this could well replace the fuel cell.

The main problem with hydrogen and particularly liquid hydrogen is the energy used to get it to liquid , 95% of all the worlds hydrogen used in mainly ammonia production comes from the steam reforming/gas shift reaction of natural gas which creates CO2 , 1000kg of liquid Hydrogen produced by this method produces 9-12 tonnes of CO2 (CO2 is quite heavy) , efficiency of energy in ammonia plants has improved but 1000kg of Ammonia uses 27,000,000 KJ , But here's the strange thing there is actually more Hydrogen in 1000m3 of Ammonia than in 1000m3  of liquid Hydrogen (146 kg of H2 in 1000m3 of Ammonia vs 71kg of H2 in 1000m3 of H2) . To keep it liquid great pressures are required for Hydrogen as well as vessels needing low thermal loss properties . A typical H2 fuel tank will need to be able to handle 350 bar which isn't far off the sorts of pressures found at the sea bed where the Titanic now rests , in old money that's 5000 lbs per sq inch.

according to IEA stats

1.4 GT of CO2 comes from the chemical industry

2.3 GT of CO2 comes from cement making (where calcium carbonate is heated/sintered driving off the CO2)

2.1 GT of CO2 from steel making

However the IEA stats don't really delve into the CO2 of steam reforming of natural gas , if we add the CO2 from oil the unit of the Barrel (around 40 us gallons 159 litrs ) produces a minimum of 317kg of CO2 and we use 95,000,000  Barrels a day.

1 Giga Tonne of CO2 is around 505,000,000m3 of CO2 , coal fired power stations put out around 10GT of CO2 globally


So back to Hydrogen , how much Hydrogen is made annually … mmm this is a tricky figure to get hold of and hoping this is correct I found 164,000,000,000 KG of H2 are produced every year mostly (95%) by steam reforming of natural gas so I get that to (9-12 tonnes of CO2 per tonne of Hydrogen) to 261 to 348 million tonnes of CO2 for making the so called clean fuel Hydrogen (or 131-175 million M3 of CO2) 


Flares , no not my fashion statement from the 1970s but the flaring of CH4 from gas and oil wells as part of the extraction process world bank report today has 150,000,000,000 m3 of natural gas flared off annually , enough to meet the gas requirements of sub Saharan Africa , which is kinda wasteful even if pretty in the night sky.


If we move to electrolysis of water current PEM technology claims to convert 75% of the electrical input , the hot alkaline variant 85% , but 1kg of Hydrogen needing 60kwh of electrical energy to make , soo 1000kg of H2 would require 60,000 kwh , so 164,000,000 tonnes of hydrogen for Ammonia I get to 9,840,000,000,000 KWh and this produces CO2 unless from a renewable source . (unsure if figure quoted is inclusive of 25% electrical loss or not if so 1kg of H2 would be 80kwh and not 60kwh)


Its getting complicated which direction to take , more electricity to make green hydrogen , more electricity to power the electric car  , hows the world going to do this ???

Well perhaps a start is for Hydrogen from water electrolysis to make Hydrogen for Ammonia then at least that's the 261-348 million tonnes of CO2 from ammonia taken care of. 

mmm 2,300,000,000 tonnes CO2 from cement making , I mean wow gee if we could only do something with that ?
Parents
  •  



    Hello Helios,



    Regarding water vapour leaving the exhaust and freezing on the road, I am with Simon Barker on this one. Toyota’s Mirai does feature a “H2O” button for the concerned driver. This enables a human to override the automated control system and choose when to dump the reaction water. In the videos it does look a bit of a silly gimmick to me, because personally and I can’t really take a world in which I need to think about taking my vehicle somewhere appropriate to ‘relieve’ itself seriously.



    ___________________________________________________________________________________________________________________________



    Good practice to question the conditions and definition of the 83% figure for efficiency. It's common to quote an ‘efficiency’ figure that makes the thing you are selling look better than competitors, after all. It's important for us all to have a good definition of what we want out of a system to be able to evaluate different technologies fairly.



    My source for this figure comes from a textbook chapter written by Professor Wolf Vielstich, a well-known German electrochemist who was awarded the Faraday medal by the Royal Society of Chemistry in 1998. The RSC acknowledging his contributions to Electrochemistry is good enough for me to believe he knows what he is talking about.


    The conditions for the 83% figure are:



    - the reactant gases are at unit pressure



    - the gases are at a constant temperature of 25 degrees centigrade



    - that the product water is entirely liquid (due to the constant temperature being 25 centigrade).



    If the reaction definition changes to say that the product water formed is entirely gaseous, this theoretical efficiency goes up, because there is no ‘work’ done to carry out the phase change. At 298 Kelvin, we get 94%, though (at least for low temperature fuel cells) the product is a mixture of the two phases and the humidity is something we have to control quite well for other reasons to do with the membranes.


    Curiously, this measure says that some electrochemical reactions give ‘efficiencies’ greater than 100%. Reacting formic acid with oxygen (HCOOH + 1/2 O2 —> CO2 + H2O) gives a theoretical efficiency of 105.6%. This tells us that at these conditions, the environment must do work to enable the reaction, rather than the reaction doing work to heat up the environment. In practice, we always need to be careful to understand what else has to be done to make the reaction work - beware claims of the perpetual motion machine!

    ___________________________________________________________________________________________________________________________



    This also partly explains why fuel cells, particularly high temperature types (the leading technology here presently being Solid Oxide Fuel Cells SOFC) are very keen on finding uses for their waste heat. If the waste heat is something you really want, then we start seeing ‘efficiencies’ up near 100% quoted for real practical systems, since then there is almost nothing ‘unwanted’ coming out of the fuel cell. Whether this heating power is always actually wanted though, is something which must be considered on a case-by-case basis:



    - The exhaust from a low temperature PEM fuel cell (approx. 60 degrees centigrade) is a good temperature for heating up the passenger area of a vehicle in the winter, but what do we do in the summer?

    - Similarly for high-temperature fuel cells, could they be linked to industrial processes which want 600+ centigrade waste heat?

    - It seems unlikely that one single technology choice will universally supersede all others.

    ___________________________________________________________________________________________________________________________



    Working pressures for hydrogen in fuel cells are on the order of a couple of bar at most (again at least for low temperature fuel cells), and much less than any kind of compressed storage which I am aware of. In this area I wonder if a technology platform like the one being developed in the UK with the support of the UK government for liquid air storage could be used to recover some of the energy when decompressing the hydrogen for use. Another interesting development is the use of membrane technologies to compress hydrogen electrochemically rather than mechanically, which offers benefits like no moving parts and the ability to run the whole process on renewable energy (if we have enough to spare).

    ___________________________________________________________________________________________________________________________



    Longevity is a problem for any new technology, especially in energy technologies. In the low-temperature world, corrosion is a limiting factor on lifespan for technologies using metallic bipolar plates in particular. Graphite based plates show superior long-term performance, but at the cost of more expensive manufacturing and thicker cells, meaning a less power dense fuel cell stack (important in some applications).


    As with everything there is a tradeoff, and plenty of work has been done and is being done to improve the long term performance of all hydrogen technologies. The typical use case for a passenger car is much less taxing than any other kind of vehicle (5000 to 6000 operating hours over the product’s life time), something which is achievable already. For almost any other application, we’re talking at least double this before we can be serious about being a long-term replacement, but if you look closely there are companies out there offering fuel cells with 20,000 operating hour expected lifespans already.



    High temperature fuel cells are can be made of tougher materials and don’t need polymer membranes, but heat cycling these units featuring metals and ceramics leads to thermal expansion problems which can cause the cell stack to become leaky and fatigue joints in the cell. Leaky hydrogen boxes aren’t anyone’s friend, but lots of clever design has been done here as well to overcome this issue, and there are plenty of examples of these in use and for sale around the world.___________________________________________________________________________________________________________________________



    If by 'peak energy system' you mean using fuel cells to replace the gas / diesel peaker plants currently used to shave off peak demand at short notice, then we're getting into the realms of frequency support and grid balancing. A combination of batteries and hydrogen energy storage could be used to replace these fossil generators, which are far more expensive and inefficient than a large CCG plant and only work out because frequency support and quickly dispatchable power is so valuable. Hydrogen is in part so interesting because HES (hydrogen energy storage) could fit into the grid both as baseload and as dispatchable peaker plant. Technically, hydrogen fits very well with a future energy grid.


    Compelling renewable generation and associated supporting (hydrogen) technologies fit the conventional centralised generation model doesn’t make the best use of what they can offer. Whether the world is too invested both economically and socially to support a change to the central generation model is something that is debated at great length. In the mean time developers of renewable generation and hydrogen technologies are working hard on making the alternative path as attractive as possible, whether we are allowed to factor in the benefits to our planet from reducing our impact on it or not.

    ___________________________________________________________________________________________________________________________


    Thanks for humouring me and for your interest in hydrogen and fuel cells!



    Cheers,



    Joe


Reply
  •  



    Hello Helios,



    Regarding water vapour leaving the exhaust and freezing on the road, I am with Simon Barker on this one. Toyota’s Mirai does feature a “H2O” button for the concerned driver. This enables a human to override the automated control system and choose when to dump the reaction water. In the videos it does look a bit of a silly gimmick to me, because personally and I can’t really take a world in which I need to think about taking my vehicle somewhere appropriate to ‘relieve’ itself seriously.



    ___________________________________________________________________________________________________________________________



    Good practice to question the conditions and definition of the 83% figure for efficiency. It's common to quote an ‘efficiency’ figure that makes the thing you are selling look better than competitors, after all. It's important for us all to have a good definition of what we want out of a system to be able to evaluate different technologies fairly.



    My source for this figure comes from a textbook chapter written by Professor Wolf Vielstich, a well-known German electrochemist who was awarded the Faraday medal by the Royal Society of Chemistry in 1998. The RSC acknowledging his contributions to Electrochemistry is good enough for me to believe he knows what he is talking about.


    The conditions for the 83% figure are:



    - the reactant gases are at unit pressure



    - the gases are at a constant temperature of 25 degrees centigrade



    - that the product water is entirely liquid (due to the constant temperature being 25 centigrade).



    If the reaction definition changes to say that the product water formed is entirely gaseous, this theoretical efficiency goes up, because there is no ‘work’ done to carry out the phase change. At 298 Kelvin, we get 94%, though (at least for low temperature fuel cells) the product is a mixture of the two phases and the humidity is something we have to control quite well for other reasons to do with the membranes.


    Curiously, this measure says that some electrochemical reactions give ‘efficiencies’ greater than 100%. Reacting formic acid with oxygen (HCOOH + 1/2 O2 —> CO2 + H2O) gives a theoretical efficiency of 105.6%. This tells us that at these conditions, the environment must do work to enable the reaction, rather than the reaction doing work to heat up the environment. In practice, we always need to be careful to understand what else has to be done to make the reaction work - beware claims of the perpetual motion machine!

    ___________________________________________________________________________________________________________________________



    This also partly explains why fuel cells, particularly high temperature types (the leading technology here presently being Solid Oxide Fuel Cells SOFC) are very keen on finding uses for their waste heat. If the waste heat is something you really want, then we start seeing ‘efficiencies’ up near 100% quoted for real practical systems, since then there is almost nothing ‘unwanted’ coming out of the fuel cell. Whether this heating power is always actually wanted though, is something which must be considered on a case-by-case basis:



    - The exhaust from a low temperature PEM fuel cell (approx. 60 degrees centigrade) is a good temperature for heating up the passenger area of a vehicle in the winter, but what do we do in the summer?

    - Similarly for high-temperature fuel cells, could they be linked to industrial processes which want 600+ centigrade waste heat?

    - It seems unlikely that one single technology choice will universally supersede all others.

    ___________________________________________________________________________________________________________________________



    Working pressures for hydrogen in fuel cells are on the order of a couple of bar at most (again at least for low temperature fuel cells), and much less than any kind of compressed storage which I am aware of. In this area I wonder if a technology platform like the one being developed in the UK with the support of the UK government for liquid air storage could be used to recover some of the energy when decompressing the hydrogen for use. Another interesting development is the use of membrane technologies to compress hydrogen electrochemically rather than mechanically, which offers benefits like no moving parts and the ability to run the whole process on renewable energy (if we have enough to spare).

    ___________________________________________________________________________________________________________________________



    Longevity is a problem for any new technology, especially in energy technologies. In the low-temperature world, corrosion is a limiting factor on lifespan for technologies using metallic bipolar plates in particular. Graphite based plates show superior long-term performance, but at the cost of more expensive manufacturing and thicker cells, meaning a less power dense fuel cell stack (important in some applications).


    As with everything there is a tradeoff, and plenty of work has been done and is being done to improve the long term performance of all hydrogen technologies. The typical use case for a passenger car is much less taxing than any other kind of vehicle (5000 to 6000 operating hours over the product’s life time), something which is achievable already. For almost any other application, we’re talking at least double this before we can be serious about being a long-term replacement, but if you look closely there are companies out there offering fuel cells with 20,000 operating hour expected lifespans already.



    High temperature fuel cells are can be made of tougher materials and don’t need polymer membranes, but heat cycling these units featuring metals and ceramics leads to thermal expansion problems which can cause the cell stack to become leaky and fatigue joints in the cell. Leaky hydrogen boxes aren’t anyone’s friend, but lots of clever design has been done here as well to overcome this issue, and there are plenty of examples of these in use and for sale around the world.___________________________________________________________________________________________________________________________



    If by 'peak energy system' you mean using fuel cells to replace the gas / diesel peaker plants currently used to shave off peak demand at short notice, then we're getting into the realms of frequency support and grid balancing. A combination of batteries and hydrogen energy storage could be used to replace these fossil generators, which are far more expensive and inefficient than a large CCG plant and only work out because frequency support and quickly dispatchable power is so valuable. Hydrogen is in part so interesting because HES (hydrogen energy storage) could fit into the grid both as baseload and as dispatchable peaker plant. Technically, hydrogen fits very well with a future energy grid.


    Compelling renewable generation and associated supporting (hydrogen) technologies fit the conventional centralised generation model doesn’t make the best use of what they can offer. Whether the world is too invested both economically and socially to support a change to the central generation model is something that is debated at great length. In the mean time developers of renewable generation and hydrogen technologies are working hard on making the alternative path as attractive as possible, whether we are allowed to factor in the benefits to our planet from reducing our impact on it or not.

    ___________________________________________________________________________________________________________________________


    Thanks for humouring me and for your interest in hydrogen and fuel cells!



    Cheers,



    Joe


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