Tag Archives: hydrogen storage

Hythane and fuel cells to power buses and trains.

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Fuel cells are highly efficient and hardly polluting. They have a long history of use in space, and as a power source for submarines. They are beginning to appear powering city buses and intercity trains, at least in Europe, but not so much in the US or Canada. The business case for fuel cells is that they provide clean electric power to the train or bus, without the need for overhead wires. Avoiding wires helps make up for the high cost of hydrogen as a fuel. The reluctance to switch to fuel cells is the US is due to the longer distances that must be covered. The very low volumetric energy density of hydrogen means you need many filling stations with hydrogen fuel cells, and many fill ups per trip.

Energy density CNG, hydrogen, hythane.

On a mass-basis, hydrogen is energy dense, with 1 kg providing the same energy as 2-3 kg of gasoline. The problem with hydrogen (aside from the cost) is that its mass density is very low, less than 50g/liter, even at high pressure. This is terribly un-dense on a volume basis. It would take 20 liters of high pressure hydrogen (about 5 gallons) to take a car or bus as far as with one gallon of gasoline. Even with a huge tank of high pressure hydrogen, 150 gallons or so, a cross country trip would require some 12 fill ups, one every 250 miles, and this is an annoyance, besides being an infrastructure problem.

Then there is cost. In California, hydrogen costs far more than gasoline, between $12 and $15 per kg. That’s ten times as expensive as gasoline on a weight basis and 4 times as expensive on an energy basis. What’s needed is a cheaper, more energy-dense version of hydrogen, ideally one that can be used in both fuel cells and IC engines, and the version I’d like to suggest is hythane, a mix of methane (natural gas) and 20-30% hydrogen.

Hythane dispenser

Hythane has about 3 times the volumetric energy density of hydrogen, and about 1/3 the price. It makes less CO and CO2 pollution because there is far less carbon. On an energy basis, hythane costs just slightly more than gasoline, and requires less infrastructure. Natural gas is cheap and available, delivered by pipeline, without the need for hydrogen delivery trucks. Because hythane has about three times the volumetric energy density of hydrogen, the tank described above, that would give a 250 mile ride with hydrogen, would give 750 miles with hythane. This means a lot fewer fueling stations are needed, and a lot fewer forced stops. As a bonus, hythane can be used in (some) IC engines as well as in fuel cells.

Hydrogen for hythane-automotive use can be made on site, by electrolysis of water. Because there is relatively little hydrogen in the mix, only 25% by volume, or 8% on an energy basis, there is relatively little burden on the electric grid, and fueling will be a lot faster than with battery chargers. Hythane is already in use in buses in China and Canada. These are normal combustion buses but hythane works even better — more efficiently — with fuel cells (solid oxide fuel cells) and thus hythane provides a path to efficiency and greater fuel cell use.

Hythane bus, Montreal.

Natural gas does not work as well in fuel cells; it requires a pre-reformer to make some H2, and even then tends to coke. To be used in most fuel cells, the methane has to be converted, at lest partially into hydrogen and this takes heat energy and water.

CH4 + H2O + energy –> 3H2 + CO

Reforming is a lot easier with hythane; it can be done within the fuel cell. Within a SOFC, the hydrogen combustion, H2 + 1/2 O2 –> H2O, provides heat and water that helps feed the reforming reaction and helps prevent coking. Long term, fuel cells will likely dominate the energy future, but for now it’s nice to have a fuel that will work well in normal IC engines too.

Robert Buxbaum, April 28, 2021

A clever, sorption-based, hydrogen compressor

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Hydrogen-powered fuel cells provide weight and cost advantages over batteries, important e.g. for drones and extended range vehicles, but they require highly compressed hydrogen and it’s often a challenge compressing the hydrogen. A large-scale solution I like is pneumatic compression, e.g. this compressor. One would combine it with a membrane reactor hydrogen generator, to fill tanks for fuel cells. The problem is that this pump is somewhat complex, and would likely add air impurities to the hydrogen. I’d now like to describe a different, very clever hydrogen pump, one that suited to smaller outputs, but adds no impurities and and provides very high pressure. It operates by metallic hydride sorption at low temperature, followed by desorption at high temperature.

Hydride sorption -desorption pressures vs temperature.

Hydride sorption -desorption pressures vs temperature, from Dhinesh et al.

The metal hydriding reaction is M + nH2 <–> MH2n. Where M is a metal or metallic alloy and MH2n is the hydride. While most metals will undergo this reaction at some appropriate temperature and pressure, the materials of practical interest are exothermic hydrides that is hydrides that give off heat on hydriding. They also must undergo a nearly stoichiometric absorption or desorption reaction at reasonable temperatures and pressures. The plot at right presents the plateau pressure for hydrogen absorption/ desorption in several, exothermic metal hydrides. The most attractive of these are shown in the red box near the center. These sorb or desorb between 1 and 10 atmospheres and 25 and 100 °C.

In this plot, the slope of the sorption line is proportional to the heat of sorption. The most attractive materials for this pump are the ones in the box (or near) with a high slope to the line implying a high heat of sorption. A high heat of sorption means you can get very high compression without too much of a temperature swing.

To me, NaAlH4 appears to be the best of the materials. Though I have not built a pump yet with this material, I’d like to. It certainly serves as a good example for how the pump might work. The basic reaction is:

NaAl + 2H2 <–> NaAlH4

suggesting that each mol of NaAl material (50g) will absorb 2 mols of hydrogen (44.8 std liters). The sorption line for this reaction crosses the 1 atm horizontal line at about 30°C. This suggests that sorption will occur at 1 am and normal room temperature: 20-25°C. Assume the pump contains 100 g of NaAl (2.0 mols). Under ideal conditions, these 100g will 4 mols of hydrogen gas, about 90 liters. If this material in now heated to 226°C, it will desorb the hydrogen (more like 80%, 72 liters) at a pressure in excess of 100 atm, or 1500 psi. The pressure line extends beyond the graph, but the sense is that one could pressure in the neighborhood of 5000 psi or more: enough to use filling the high pressure tank of a hydrogen-based, fuel cell car.

The problem with this pump for larger volume H2 users is time. It will take 2-3 hours to cycle the sober, that is, to absorb hydrogen at low pressure, to heat the material to 226°C, to desorb the H2 and cycle back to low temperature. At a pump rate of 72 liters in 2-3 hours, this will not be an effective pump for a fuel-cell car. The output, 72 liters is only enough to generate 0.12kWh, perhaps enough for the tank of a fuel cell drone, or for augmenting the mpg of gasoline automobiles. If one is interested in these materials, my company, REB Research will be happy to manufacture some in research quantities (the prices blow are for materials cost, only I will charge significantly more for the manufactured product, and more yet if you want a heater/cooler system).

Properties of Metal Hydride materials; Dhanesh Chandra,* Wen-Ming Chien and Anjali Talekar, Material Matters, Volume 6 Article 2

Properties of Metal Hydride materials; Dhanesh Chandra,* Wen-Ming Chien and Anjali Talekar, Material Matters, Volume 6 Article 2

One could increase the output of a pump by using more sorbent, perhaps 10 kg distributed over 100 cells. With this much sorbent, you’ll pump 100 times faster, enough to take the output of a fairly large hydrogen generator, like this one from REB. I’m not sure you get economies of scale, though. With a mechanical pump, or the pneumatical pump,  you get an economy of scale: typically it costs 3 times as much for each 10 times increase in output. For the hydride pump, a ten times increase might cost 7-8 times as much. For this reason, the sorption pump lends itself to low volume applications. At high volume, you’re going to want a mechanical pump, perhaps with a getter to remove small amounts of air impurities.

Materials with sorption lines near the middle of the graph above are suited for long-term hydrogen storage. Uranium hydride is popular in the nuclear industry, though I have also provided Pd-coated niobium for this purpose. Materials whose graph appear at the far, lower left, titanium TiH2, can be used for permanent hydrogen removal (gettering). I have sold Pd-niobium screws for this application, and will be happy to provide other shapes and other materials, e.g. for reversible vacuum pumping from a fusion reactor.

Robert Buxbaum, May 26, 2017 (updated Apr. 4, 2022). 

The hydrogen jerrycan

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Here’s a simple invention, one I’ve worked on off-and-on for years, but never quite built. I plan to work on it more this summer, and may finally build a prototype: it’s a hydrogen Jerry can. The need to me is terrifically obvious, but the product does not exist yet.

To get a view of the need, imagine that it’s 5-10 years in the future and you own a hydrogen, fuel cell car. You’ve run out of gas on a road somewhere, per haps a mile or two from the nearest filling station, perhaps more. You make a call to the AAA road-side service and they show up with enough hydrogen to get you to the next filling station. Tell me, how much hydrogen did they bring? 1 kg, 2 kg, 5 kg? What did the container look like? Is there one like it in your garage?

The original, German "Jerry" can. It was designed at the beginning of WWII to help the Germans to overrun Europe.

The original, German “Jerry” can. It was designed at the beginning of WWII to help the Germans to overrun Europe. I imagine the hydrogen version will be red and roughly these dimensions, though not quite this shape.

I figure that, in 5-10 years these hydrogen containers will be so common that everyone with a fuel cell car will have one, somewhere. I’m pretty confident too that hydrogen cars are coming soon. Hydrogen is not a total replacement for gasoline, but hydrogen energy provides big advantages in combination with batteries. It really adds to automotive range at minimal cost. Perhaps, of course this is wishful thinking as my company makes hydrogen generators. Still it seems worthwhile to design this important component of the hydrogen economy.

I have a mental picture of what the hydrogen delivery container might look like based on the “Jerry can” that the Germans (Jerrys) developed to hold gasoline –part of their planning for WWII. The story of our reverse engineering of it is worth reading. While the original can was green for camouflage, modern versions are red to indicate flammable, and I imagine the hydrogen Jerry will be red too. It must be reasonably cheap, but not too cheap, as safety will be a key issue. A can that costs $100 or so does not seem excessive. I imagine the hydrogen Jerry can will be roughly rectangular like the original so it doesn’t roll about in the trunk of a car, and so you can stack a few in your garage, or carry them conveniently. Some folks will want to carry an extra supply if they go on a long camping trip. As high-pressure tanks are cylindrical, I imagine the hydrogen-jerry to be composed of two cylinders, 6 1/2″ in diameter about. To make the rectangular shape, I imagine the cylinders attached like the double pack of a scuba diver. To match the dimensions of the original, the cylinders will be 14″ to 20″ tall.

I imagine that the hydrogen Jerry can will have at least two spouts. One spout so it can be filled from a standard hydrogen dispenser, and one so it can be used to fill your car. I suspect there may be an over-pressure relief port as well, for safety. The can can’t be too heavy, no more than 33 lbs, 15 kg when full so one person can handle it. To keep the cost and weight down, I imagine the product will be made of marangeing steel wrapped in kevlar or carbon fiber. A 20 kg container made of these materials will hold 1.5 to 2 kg of hydrogen, the equivalent of 2 gallons of gasoline.

I imagine that the can will have at least one handle, likely two. The original can had three handles, but this seems excessive to me. The connection tube between two short cylinders could be designed to serve as one of the handles. For safety, the Jerrycan should have a secure over-seal on both of the fill-ports, ideally with a safety pin latch minimize trouble in a crash. All the parts, including the over- seal and pin, should be attached to the can so that they are not easily lost. Do you agree? What else, if anything, do you imagine?

Robert Buxbaum, February 26, 2017. My company, REB Research, makes hydrogen generators and purifiers.

Advanced windmills + 20 years = field of junk

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Everything wears out. This can be a comforting or a depressing thought, but it’s a truth. No old mistake, however egregious, lasts forever, and no bold advance avoids decay. At best, last year’s advance will pay for itself with interest, will wear out gracefully, and will be recalled fondly by aficionados after it’s replaced by something better. Water wheels, and early steamships are examples of this type of bold advance. Unfortunately, it is often the case that last years innovation turns out to be no advance at all: a technological dead end that never pays for itself, and becomes a dangerous, rotting eyesore or worse, a laughing-stock blot or a blot on the ecology. Our first two generations of advanced windmill farms seem to match this description; perhaps the next generation will be better, but here are some thoughts on lessons learned from the existing fields of rotting windmills.

The ancient design windmills of Don Quixote’s Spain (1300?) were boons. Farmers used them to grind grain or cut wood, and to to pump drinking water. Holland used similar early windmills to drain their land. So several American presidents came to believe advanced design windmills would be similar boons if used for continuous electric power generation. It didn’t work, and many of the problems could have been seen at the start. While the farmer didn’t care when his water was pumped, or when his wood is cut. When you’re generating electricity, there is a need to match the power demand exactly. Whenever the customer turns on the switch, electricity is expected to flow at the appropriate amount of Wattage; at other times any power generated is a waste or a nuisance. But electric generator-windmills do not produce power on demand, they produce power when the wind blows. The mismatch of wind and electric demand has bedeviled windmill reliability and economic return. It will likely continue to do so until we find a good way to store electric power cheaply. Until then windmills will not be able to produce electricity at competitive prices to compete with cheap coal and nuclear power.

There is also the problem of repair. The old windmills of Holland still turn a century later because they were relatively robust, and relatively easy to maintain. The modern windmills of the US stand much taller and move much faster. They are often hit, and damaged by lightning strikes, and their fast-turning gears tend to wear out fast, Once damaged, modern windmills are not readily fix, They are made of advanced fiberglass materials spun on special molds. Worse yet, they are constructed in mountainous, remote locations. Such blades can not be replaces by amateurs, and even the gears are not readily accessed to repair. More than half of the great power-windmills built in the last 35 years have worn out and are unlikely to ever get repair. Driving past, you see fields of them sitting idle; the ones still turning look like they will wear out soon. The companies that made and installed these behemoth are mostly out of the business, so there is no-one there to take them down even if there were an economic incentive to do so. Even where a company is found to fix the old windmills, no one would as there is not sufficient economic return — the electricity is worth less than the repair.

Komoa Wind Farm in Kona, Hawaii June 2010; Friends of Grand Ronde Valley.

Komoa Wind Farm in Kona, Hawaii, June 2010; A field of modern design wind-turbines already ruined by wear, wind, and lightning. — Friends of Grand Ronde Valley.

A single rusting windmill would be bad enough, but modern wind turbines were put up as wind farms with nominal power production targeted to match the output of small coal-fired generators. These wind farms require a lot of area,  covering many square miles along some of the most beautiful mountain ranges and ridges — places chosen because the wind was strong

Putting up these massive farms of windmills lead to a situation where the government had pay for construction of the project, and often where the government provided the land. This, generous spending gives the taxpayer the risk, and often a political gain — generally to a contributor. But there is very little political gain in paying for the repair or removal of the windmills. And since the electricity value is less than the repair cost, the owners (friends of the politician) generally leave the broken hulks to sit and rot. Politicians don’t like to pay to fix their past mistakes as it undermines their next boondoggle, suggesting it will someday rust apart without ever paying for itself.

So what can be done. I wish I could suggest less arrogance and political corruption, but I see no way to achieve that, as the poet wrote about Ozymandias (Ramses II) and his disastrous building projects, the leader inevitably believes: “I am Ozymandias, king of kings; look on my works ye mighty and despair.” So I’ll propose some other, less ambitious ideas. For one, smaller demonstration projects closer to the customer. First see if a single windmill pays for itself, and only then build a second. Also, electricity storage is absolutely key. I think it is worthwhile to store excess wind power as hydrogen (hydrogen storage is far cheaper than batteries), and the thermodynamics are not bad

Robert E. Buxbaum, January 3, 2016. These comments are not entirely altruistic. I own a company that makes hydrogen generators and hydrogen purifiers. If the government were to take my suggestions I would benefit.

Hydrogen cars and buses are better than Tesla

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Hydrogen fueled cars and buses are as clean to drive as battery vehicles and have better range and faster fueling times. Cost-wise, a hydrogen fuel tank is far cheaper and lighter than an equivalent battery and lasts far longer. Hydrogen is likely safer because the tanks do not carry their oxidant in them. And the price of hydrogen is relatively low, about that of gasoline on a per-mile basis: far lower than batteries when the cost of battery wear-out is included. Both Presidents Clinton and Bush preferred hydrogen over batteries, but the current administration favors batteries. Perhaps history will show them correct, but I think otherwise. Currently, there is not a hydrogen bus, car, or boat making runs at Disney’s Experimental Community of Tomorrow (EPCOT), nor is there an electric bus car or boat. I suspect it’s a mistake, at least convening the lack of a hydrogen vehicle. 

The best hydrogen vehicles on the road have more range than the best electric vehicle, and fuel faster. The hydrogen powered, Honda Clarity debuted in 2008. It has a 270 mile range and takes 3-5 minutes to fuel with hydrogen at 350 atm, 5150 psi. By contrast, the Tesla S-sedan that debuted in 2012 claims only a 208 mile range for its standard, 60kWh configuration (the EPA claims: 190 miles) and requires three hours to charge using their fastest charger, 20 kW.

What limits the range of battery vehicles is that the stacks are very heavy and expensive. Despite using modern lithium-ion technology, Tesla’s 60 kWh battery weighs 1050 lbs including internal cooling, and adds another 250 lbs to the car for extra structural support. The Clarity fuel system weighs a lot less. The hydrogen cylinders weigh 150 lb and require a fuel cell stack (30 lb) and a smaller lithium-ion battery for start-up (90 lb). The net effect is that the Clarity weighs 3582 lbs vs 4647 lbs for the Tesla S. This extra weight of the Tesla seems to hurt its mileage by about 10%. The Tesla gets about 3.3 mi/kWh or 0.19 mile/lb of battery versus 60 miles/kg of hydrogen for the Clarity suggesting  3.6 mi/kWh at typical efficiencies. 

High pressure hydrogen tanks are smaller than batteries and cheaper per unit range. The higher the pressure the smaller the tank. The current Clarity fuels with 350 atm, 5,150 psi hydrogen, and the next generation (shown below) will use higher pressure to save space. But even with 335 atm hydrogen (5000 psi) a Clarity could fuel a 270 mile range with four, 8″ diameter tanks (ID), 4′ long. I don’t know how Honda makes its hydrogen tanks, but suitable tanks might be made from 0.065″ Maranging (aged) stainless steel (UTS = 350,000 psi, density 8 g/cc), surrounded by 0.1″ of aramid fiber (UTS = 250,000 psi, density = 1.6 g/cc). With this construction, each tank would weigh 14.0 kg (30.5 lbs) empty, and hold 11,400 standard liters, 1.14 kg (2.5 lb) of hydrogen at pressure. These tanks could cost $1500 total; the 270 mile range is 40% more Than the Tesla S at about 1/10 the cost of current Tesla S batteries The current price of a replacement Tesla battery pack is $12,000, subsidized by DoE; without the subsidy, the likely price would be $40,000.

Next generation Honda fuel cell vehicle prototype at the 2014 Detroit Auto Show.

Next generation Honda fuel cell vehicle prototype at the 2014 Detroit Auto Show.

Currently hydrogen is more expensive than electricity per energy value, but my company has technology to make it cheaply and more cleanly than electricity. My company, REB Research makes hydrogen generators that produce ultra pure hydrogen by steam reforming wow alcohol in a membrane reactor. A standard generator, suitable to a small fueling station outputs 9.5 kg of hydrogen per day, consuming 69 gal of methanol-water. At 80¢/gal for methanol-water, and 12¢/kWh for electricity, the output hydrogen costs $2.50/kg. A car owner who drove 120,000 miles would spend $5,000 on hydrogen fuel. For that distance, a Tesla owner would spend only $4400 on electricity, but would have to spend another $12,000 to replace the battery. Tesla batteries have a 120,000 mile life, and the range decreases with age. 

For a bus or truck at EPCOT, the advantages of hydrogen grow fast. A typical bus is expected to travel much further than 120,000 miles, and is expected to operate for 18 hour shifts in stop-go operation getting perhaps 1/4 the miles/kWh of a sedan. The charge time and range advantages of hydrogen build up fast. it’s common to build a hydrogen bus with five 20 foot x 8″ tanks. Fueled at 5000 psi., such buses will have a range of 420 miles between fill-ups, and a total tank weight and cost of about 600 lbs and $4000 respectively. By comparison, the range for an electric bus is unlikely to exceed 300 miles, and even this will require a 6000 lb., 360 kWh lithium-ion battery that takes 4.5 hours to charge assuming an 80 kW charger (200 Amps at 400 V for example). That’s excessive compared to 10-20 minutes for fueling with hydrogen.

While my hydrogen generators are not cheap: for the one above, about $500,000 including the cost of a compressor, the cost of an 80 kW DC is similar if you include the cost to run a 200 Amp, 400 V power line. Tesla has shown there are a lot of people who value clean, futuristic transport if that comes with comfort and style. A hydrogen car can meet that handily, and can provide the extra comforts of longer range and faster refueling.

Robert E. Buxbaum, February 12, 2014 (Lincoln’s birthday). Here’s an essay on Lincoln’s Gettysburg address, on the safety of batteries, and on battery cost vs hydrogen. My company, REB Research makes hydrogen generators and purifiers; we also consult.