Germany’s green transition is a disaster. Twenty years ago, Germany had 23 nuclear power plants that generated 30% of the country’s electricity cleanly, cheaply, and reliably. These plants have all been shut by the government as part of a commitment to clean energy. What could be cleaner? Germany has switched to a mix of wind and solar, plus a significant shift to coal power. Wind and solar use a lot of land compared to nuclear, and they break down leaving fields of debris. There is now a lack of electricity to power homes and industries, and what power there is, is unreliable, due to the many dark windless days in Germany.
The lack of reliable electricity is crippling German industry now that Russian gas has been cut off. In this environment, why would the Germans order special trains and boats that burn, hydrogen that’s made from electricity and natural gas? My understanding of the reason is that, Germany sometimes has too much wind power and nothing to do with it. They plan to store this excess by making hydrogen that they can use to power their trains and boats. The cost is high, and the efficiency is poor, but the electricity is free.
Hydrogen is not as compact a fuel as gasoline, nor is it as cheap as electricity, but it’s cleaner than gas, and in some ways it’s better than battery-stored electricity. While hydrogen takes a lot of storage space relative to gasoline, high pressure helps, and the storage is cheaper than with batteries. Also, hydrogen fuel is transferred faster than electric fuels. Trains and ships are chosen for hydrogen because they are good at carrying bulky items. The transition to hydrogen is relatively straightforward with trains, since many are already powered by electricity. Hydrogen fuel cells can make the electricity on board (in theory), while avoiding the need for expensive overhead wires. The idea sort-of makes sense.
Germany’s first hydrogen train. cancelled after 1 year of poor operating.
The first German train to use hydrogen powered them with fuel cells that generated electricity. It began service in October 2022, but the fuel cells proved unreliable. Service ended one year later, October 2023, replaced by polluting diesel (see here). The Hannover line plans to replace these with battery-powered trains over the next few years. There are also plans for a hydrogen-powered ferry, but it is not clear why the ferry should prove more reliable than the train, or cheaper.
San Francisco’s hydrogen-powered ferry, $30 million, 15 knots top speed, 75 passengers, no cars. Long delayed.
In the US, the Biden administration has paid, so far, $30 million for a hydrogen ferry in San Francisco. It’s two years behind schedule and over cost, taking only 75 passengers and no cars at 15 knots, 17mph. In the US, and likely in Germany, most of the hydrogen will be made from natural gas. A better solution, I think would be to power the ferris and trains by natural gas and to store the excess electricity in land-based batteries or as land-based hydrogen for land-based fuel cells.
Germany is committed to electric trains, though, and hydrogen provides a route to power these trains with excess electricity. German customers take the train, in part, because they like them, and in part because German politicians have banned short-hop planes on competing routes, and subsidized electric trains. Yet another option to balance times of excess solar and wind power would be to subsidize electric cars, or at least allow theirs owners to trade electricity: to buy electricity when it’s cheap and resell it to the grid when demand and prices are high.
Heat exchange is a key part of most chemical process designs. Heat exchangers save money because they’re generally cheaper than heaters and the continuing cost of fuel or electricity to run the heaters. They also usually provide free, fast cooling for the product; often the product is made hot, and needs to be cooled. Hot products are usually undesirable. Free, fast cooling is good.
So how do you design a heat exchanger? A common design is to weld the right amount of tubes inside a shell, so it looks like the drawing below. The the hot fluid might be made to go through the tubes, and the cold in the shell, as shown, or the hot can flow through the shell. In either case, the flows are usually in the opposite direction so there is a hot end and a cold end as shown. In this essay, I’d like to discuss how I design our counter current heat exchangers beginning a common case (for us) where the two flows have the same thermal inertia, e.g. the same mass flow rates and the same heat capacities. That’s the situation with our hydrogen purifiers: impure hydrogen goes in cold, and is heated to 400°C for purification. Virtually all of this hot hydrogen exits the purifier in the “pure out” stream and needs to be cooled to room temperature or nearly.
Typical shell and tube heat exchanger design, Black Hills inc.
For our typical designs the hot flows in one direction, and an equal cold flow is opposite, I will show the temperature difference is constant all along the heat exchanger. As a first pass rule of thumb, I design so that this constant temperature difference is 30°C. That is ∆THX =~ 30°C at every point along the heat exchanger. More specifically, in our Mr Hydrogen® purifiers, the impure, feed hydrogen enters at 20°C typically, and is heated by the heat exchanger to 370°C. That is 30°C cooler than the final process temperature. The hydrogen must be heated this last 30°C with electricity. After purification, the hot, pure hydrogen, at 400°C, enters the heat exchanger leaving at 30°C above the input temperature, that is at 50°C. It’s hot, but not scalding. The last 30°C of cooling is done with air blown by a fan.
The power demand of the external heat source, the electric heater, is calculated as: Wheater = flow (mols/second)*heat capacity (J/°C – mol)* (∆Theater= ∆THX = 30°C).
The smaller the value of ∆THX, the less electric draw you need for steady state operation, but the more you have to pay for the heat exchanger. For small flows, I often use a higher value of ∆THX = 30°C, and for large flows smaller, but 30°C is a good place to start.
Now to size the heat exchanger. Because the flow rate of hot fluid (purified hydrogen) is virtually the same as for cold fluid (impure hydrogen), the heat capacity per mol of product coming out is the same as for mol of feed going in. Since enthalpy change equals heat capacity time temperature change, ∆H= Cp∆T, with effectiveCp the same for both fluids, and any rise in H in the cool fluid coming at the hot fluid, we can draw a temperature vs enthalpy diagram that will look like this:
The heat exchanger heats the feed from 20°C to 370°C. ∆T = 350°C. It also cools the product 350°C, that is from 400 to 50°C. In each case the enthalpy exchanged per mol of feed (or product is ∆H= Cp*∆T = 7*350 =2450 calories.
Since most heaters work in Watts, not calories, at some point it’s worthwhile to switch to Watts. 1 Cal = 4.174 J, 1 Cal/sec = 4.174 W. I tend to do calculations in mixed units (English and SI) because the heat capacity per mole of most things are simple numbers in English units. Cp (water) for example = 1 cal/g = 18 cal/mol. Cp (hydrogen) = 7 cal/mol. In SI units, the heat rate, WHX, is:
The flow rate in mols per second is the flow rate in slpm divided by 22.4 x 60. Since the driving force for transfer is 30°C, the area of the heat exchanger is WHX times the resistance divided by ∆THX:
A = WHX * R / 30°C.
Here, R is the average resistance to heat transfer, m2*∆T/Watt. It equals the sum of all the resistances, essentially the sum of the resistance of the steel of the heat exchanger plus that of the two gas phases:
R= δm/km + h1+ h2
Here, δm is the thickness of the metal, km is the thermal conductivity of the metal, and h1 and h2 are the gas-phase heat transfer parameters in the feed and product flow respectively. You can often estimate these as δ1/k1 and δ2/k2 respectively, with k1 and k2 as the thermal conductivity of the feed and product, both hydrogen in my case. As for, δ, the effective gas-layer thickness, I generally estimate this as 1/3 the thickness of the flow channel, for example:
h1 = δ1/k1 = 1/3 D1/k1.
Because δ is smaller the smaller the diameter of the tubes, h is smaller too. Also small tubes tend to be cheaper than big ones, and more compact. I thus prefer to use small diameter tubes and small diameter gaps. in my heat exchangers, the tubes are often 1/4″ or bigger, but the gap sizes are targeted to 1/8″ or less. If the gap size gets too low, you get excessive pressure drops and non-uniform flow, so you have to check that the pressure drop isn’t too large. I tend to stick to normal tube sizes, and tweak the design a few times within those parameters, considering customer needs. Only after the numbers look good to my aesthetics, do I make the product. Aesthetics plays a role here: you have to have a sense of what a well-designed exchanger should look like.
The above calculations are fine for the simple case where ∆THX is constant. But what happens if it is not. Let’s say the feed is impure, so some hot product has to be vented, leaving les hot fluid in the heat exchanger than feed. I show this in the plot at right for the case of 14% impurities. Sine there is no phase change, the lines are still straight, but they are no longer parallel. Because more thermal mass enters than leaves, the hot gas is cooled completely, that is to 50°C, 30°C above room temperature, but the cool gas is heated at only 7/8 the rate that the hot gas is cooled. The hot gas gives off 2450 cal as before, but this is now only enough to heat the cold fluid by 2450/8 = 306.5°. The cool gas thus leave the heat exchanger at 20°C+ 306.8° = 326.5°C.
The simple way to size the heat exchanger now is to use an average value for ∆THX. In the diagram, ∆THX is seen to vary between 30°C at the entrance and and 97.5°C at the exit. As a conservative average, I’ll assume that ∆THX = 40°C, though 50 to 60°C might be more accurate. This results in a small heat exchanger design that’s 3/4 the size of before, and is still overdesigned by 25%. There is no great down-side to this overdesign. With over-design, the hot fluid leaves at a lower ∆THX, that is, at a temperature below 50°C. The cold fluid will be heated to a bit more than to the 326.5°C predicted, perhaps to 330°C. We save more energy, and waste a bit on materials cost. There is a “correct approach”, of course, and it involves the use of calculous. A = ∫dA = ∫R/∆THX dWHX using an analytic function for ∆THX as a function of WHX. Calculating this way takes lots of time for little benefit. My time is worth more than a few ounces of metal.
The only times that I do the correct analysis is with flame boilers, with major mismatches between the hot and cold flows, or when the government requires calculations. Otherwise, I make an H Vs T diagram and account for the fact that ∆T varies with H is by averaging. I doubt most people do any more than that. It’s not like ∆THX = 30°C is etched in stone somewhere, either, it’s a rule of thumb, nothing more. It’s there to make your life easier, not to be worshiped.
The hydrogen economy is generally thought to come in some distant future, where your car (and perhaps your home) runs on hydrogen, and the hydrogen, presumably, is made by clean nuclear or renewable solar or wind power. This is understood to be better than the current state of things where your car runs on dirty gasoline, and your home runs on coal or gas, except when the sun is shining bright and the wind is blowing hard. Our homes and cars can not run on solar or wind alone, although solar cells have become quite cheap, because solar power is only available in the daytime, basically for 6 hours, from about 9AM to 3PM. Hydrogen has been proposed as a good way to store solar and wind energy that you can’t use, but it’s not easy to store hydrogen — or is it? I’d like to suggest that, to a decent extent, we already store green hydrogen and use it to run our trucks. We store this hydrogen in the form of Diesel fuel, so you don’t realize it’s hydrogen.
Much of the oil in the United States these days comes from tar sands and shale. It doesn’t flow well at room temperature, and is too heavy and gooey for normal use. We could distill this crude oil and use only the light parts, but that would involve throwing away a huge majority of the oil. Instead we steam reform it to gasoline, ethylene and other products. The reaction is something like this, presuming an input feed of naphtha, C10H8:
C10H8 + 2 H2O –> C7H8 + C2H4 + CO2.
The C2H4 component is ethylene. We use it to make plastics. The C7H8 is called toluene. It is a component of high octane gasoline (octane rating about 114). The inventor of the process, Eugene Jules Houdry claimed to have won WWII for the allies because his secret process (Houdryflow catalytic cracking) allowed high production of lots of gasoline of very high octane, giving US and British planes and trucks higher mpg than the Germans or Japanese had. It was a great money maker, but companies can make even more by adding hydrogen.
Schematic of the hydrocracking process, from the US energy information agency
Over the last 2-3 decades, refineries have been adding catalytic hydrogenation processes. These convert high octane aromatic products, like toluene to low -octane diesel and jet fuel. These products sell for more. Aromatic toluene is exposed to hydrogen at about 500°C and 300 psi (20 bar) to produce heptane, an excellent diesel fuel with about 7% more energy content than toluene per gallon.
C7H8 + 4H2 –> C7H16.
Diesel fuel sell for about 20% more than gasoline per gallon, in part because of the higher energy content, and because Diesel engines are more efficient than gas engines. What’s more, toluene expands as it’s converted to heptane. One gallon of toluene converts to 1.16 gallons of heptane. As a result hydrogenation adds about 40% to the sales price per molecule. Refineries have found that they can make significant money this way if they can buy cheap hydrogen. Over the last few years, several refineries in Norway and Texas (high sun and wind areas) have added hydrogenators along with electrolysis units to produce the cheap hydrogen when no one needs the unwanted electricity generated when supply exceeds demand. Here is an analysis of the thermodynamics of this type of hydrogen generation.
The main products of my company, REB Research, involve metallic membranes, often palladium-based, that provide 100% selective hydrogen filtering or long term hydrogen storage. One way to understand why these metallic membrane provide 100% selectivity has to do with the fact that metallic atoms are much bigger than hydrogen ions, with absolutely regular, small spaces between them that fit hydrogen and nothing else.
Palladium atoms are essentially spheres. In the metallic form, the atoms pack in an FCC structure (face-centered cubic) with a radius of, 1.375 Å. There is a cloud of free electrons that provide conductivity and heat transfer, but as far as the structure of the metal, there is only a tiny space of 0.426 Å between the atoms, see below. This hole is too small of any molecule, or any inert gas. In the gas phase hydrogen molecules are about 1.06 Å in diameter, and other molecules are bigger. Hydrogen atoms shrink when inside a metal, though, to 0.3 to 0.4 Å, just small enough to fit through the holes.
The reason that hydrogen shrinks has to do with its electron leaving to join palladium’s condition cloud. Hydrogen is usually put on the upper left of the periodic table because, in most cases, it behaves as a metal. Like a metal, it reacts with oxygen, and chlorine, forming stoichiometric compounds like H2O and HCl. It also behaves like a metal in that it alloys, non-stoichiometrically, with other metals. Not with all metals, but with many, Pd and the transition metals in particular. Metal atoms are a lot bigger than hydrogen so there is little metallic expansion on alloying. The hydrogen fits in the tiny spaces between atoms. I’ve previously written about hydrogen transport through transition metals (we provide membranes for this too).
No other atom or molecule fits in the tiny space between palladium atoms. Other atoms and molecules are bigger, 1.5Å or more in size. This is far too big to fit in a hole 0.426Å in diameter. The result is that palladium is basically 100% selective to hydrogen. Other metals are too, but palladium is particularly good in that it does not readily oxidize. We sometime sell transition metal membranes and sorbers, but typically coat the underlying metal with palladium.
We don’t typically sell products of pure palladium, by the way. Instead most of our products use, Pd-25%Ag or Pd-Cu. These alloys are slightly cheaper than pure Pd and more stable. Pd-25% silver is also slightly more permeable to hydrogen than pure Pd is — a win-win-win for the alloy.
My favorite fuel cells burn hydrogen-rich hydrocarbon fuels, like methane (natural gas) instead of pure hydrogen. Methane is far more energy dense, and costs far less than hydrogen per energy content. The US has plenty of methane and has pipelines that distribute it to every city and town. It’s a low CO2 fuel, and we can lower the CO2 impact further by mixing in hydrogen to get hythane. Elon Musk has called hydrogen- powered fuel cells “fool cells”, methane-powered fuel cells look a lot less foolish. They easily compete with his batteries and with gasoline. Besides, Musk has chosen methane as the fuel for his proposed starship to Mars.
Solid oxide fuel cells, SOFCs, can use methane directly without any pre-reformer. They operate at 800°C or so. At these temperatures, methane reacts with water (steam) within the fuel cell to form hydrogen by the reaction, CH4 + H2O –> 3H2 + CO. The hydrogen, and to a lesser extent the CO is oxidized in the fuel cell to create electricity,, but the methane is not 100% consumed, generally. Unused methane, CO, and some hydrogen exits a solid oxide fuel cell along with the products of combustion, CO2 and water.
Several researchers have looked for ways to recycle this waste fuel to capture the energy value. Six years ago, I patented a membrane method to extract the waste fuel and recycle it, see a description here. I now see this method as too complex, and have applied for a patent on a simpler version, shown below as Figure 1. As before the main work is done by a membrane but here I dispense with the water gas shift reactor, and many of the heat exchangers of the previous approach.
Simple way to improve fuel use in a high temperature fuel cell, using just a membrane.
The fuel cell system of Fig. 1 operates at somewhat elevated pressure, 2 atm or more. It is expected that the majority of the exhaust going to the membrane will be CO2 and water. Most of this will pass through the membrane and will exhaust to the air. The rest is mixed with fresh methane and recycles to the fuel cell. Despite the pressure of the fuel cell, very a little energy is needed for recirculation since the methane does not go through the membrane. The result is a light, simple, and energy efficient process. If you are interested, please contact me at REB Research. Or you can purchase the silicone membrane module here. Alternately, see here for flux information and other applications.
A hydrogen molecule consists of two protons held together by a covalent bond. One way to think of such bonds is to imagine that there is only one electron is directly involved as shown below. The bonding electron only spends 1/7 of its time between the protons, making the bond, the other 6/7 of the time the electron shields the two protons by 3/7 e– each, reducing the effective charge of each proton to 4/7e+.
We see that the two shielded protons will repel each other with the force of FR = Ke (16/49 e2 /r2) where e is the charge of an electron or proton, r is the distance between the protons (r = 0.74Å = 0.74×10-10m), and Ke is Coulomb’s electrical constant, Ke ≈ 8.988×109 N⋅m2⋅C−2. The attractive force is calculated similarly, as each proton attracts the central electron by FA = – Ke (4/49) e2/ (r/2)2. The forces are seen to be in balance, the net force is zero.
It is because of quantum mechanics, that the bond is the length that it is. If the atoms were to move closer than r = 0.74Å, the central electron would be confined to less space and would get more energy, causing it to spend less time between the two protons. With less of an electron between them, FR would be greater than FA and the protons would repel. If the atoms moved further apart than 0.74Å, a greater fraction of the electron would move to the center, FA would increase, and the atoms would attract. This is a fairly pleasant way to understand why the hydrogen side of all hydrogen covalent bonds are the same length. It’s also a nice introduction to muon-catalyzed cold fusion.
Most fusion takes place only at high temperatures, at 100 million °C in a TOKAMAK Fusion reactor, or at about 15 million °C in the high pressure interior of the sun. Muon catalyzed fusion creates the equivalent of a much higher pressure, so that fusion occurs at room temperature. The trick to muon catalyzed fusion is to replace one of the electrons with a muon, an unstable, heavy electron particle discovered in 1936. The muon, designated µ-, behaves just like an electron but it has about 207 times the mass. As a result when it replaces an electron in hydrogen, it forms form a covalent bond that is about 1/207th the length of a normal bond. This is the equivalent of extreme pressure. At this closer distance, hydrogen nuclei fuse even at room temperature.
In normal hydrogen, the nuclei are just protons. When they fuse, one of them becomes a neutron. You get a deuteron (a proton-neutron pair), plus an anti electron and 1.44 MeV of energy after the anti-electron has annihilated (for more on antimatter see here). The muon is released most of the time, and can catalyze many more fusion reactions. See figure at right.
While 1.44MeV per reaction is a lot by ordinary standards — roughly one million times more energy than is released per atom when hydrogen is burnt — it’s very little compared to the energy it takes to make a muon. Making a muon takes a minimum of 1000 MeV, and more typically 4000 MeV using current technology. You need to get a lot more energy per muon if this process is to be useful.
You get quite a lot more energy when a muon catalyzes deuterium fusion or deuterium- fusion. With these reactions, you get 3.3 to 4 MeV worth of energy per fusion, and the muon will be ejected with enough force to support about eight D-D fusions before it decays or sticks to a helium atom. That’s better than before, but still not enough to justify the cost of making the muon.
The next reactions to consider are D-T fusion and Li-D fusion. Tritium is an even heavier isotope of hydrogen. It undergoes muon catalyzed fusion with deuterium via the reaction, D+T –> 4He +n +17.6 MeV. Because of the higher energy of the reaction, the muons are even less likely to stick to a helium atom, and you get about 100 fusions per muon. 100 x 17.6 MeV = 1.76 GeV, barely break-even for the high energy cost to make the muon, but there is no reason to stop there. You can use the high energy fusion neutrons to catalyze LiD fusion. For example, 2LiD +n –> 34He + T + D +n producing 19.9 MeV and a tritium atom.
With this additional 19.9 MeV per DT fusion, the system can start to produce usable energy for sale. It is also important that tritium is made in the process. You need tritium for the fusion reactions, and there are not many other supplies. The spare neutron is interesting too. It can be used to make additional tritium or for other purposes. It’s a direction I’d like to explore further. I worked on making tritium for my PhD, and in my opinion, this sort of hybrid operation is the most attractive route to clean nuclear fusion power.
There are two ASTM-approved methods for measuring the gas permeability of a material. The equipment is very similar, and REB Research makes equipment for either. In one of these methods (described in detail here) you measure the rate of pressure rise in a small volume.This method is ideal for high permeation rate materials. It’s fast, reliable, and as a bonus, allows you to infer diffusivity and solubility as well, based on the permeation and breakthrough time.
Exploded view of the permeation cell.
For slower permeation materials, I’ve found you are better off with the other method: using a flow of sampling gas (helium typically, though argon can be used as well) and a gas-sampling gas chromatograph. We sell the cells for this, though not the gas chromatograph. For my own work, I use helium as the carrier gas and sampling gas, along with a GC with a 1 cc sampling loop (a coil of stainless steel tube), and an automatic, gas-operated valve, called a sampling valve. I use a VECO ionization detector since it provides the greatest sensitivity differentiating hydrogen from helium.
When doing an experiment, the permeate gas is put into the upper chamber. That’s typically hydrogen for my experiments. The sampling gas (helium in my setup) is made to flow past the lower chamber at a fixed, flow rate, 20 sccm or less. The sampling gas then flows to the sampling loop of the GC, and from there up the hood. Every 20 minutes or so, the sampling valve switches, sending the sampling gas directly out the hood. When the valve switches, the carrier gas (helium) now passes through the sampling loop on its way to the column. This sends the 1 cc of sample directly to the GC column as a single “injection”. The GC column separates the various gases in the sample and determines the components and the concentration of each. From the helium flow rate, and the argon concentration in it, I determine the permeation rate and, from that, the permeability of the material.
As an example, let’s assume that the sample gas flow is 20 sccm, as in the diagram above, and that the GC determines the H2 concentration to be 1 ppm. The permeation rate is thus 20 x 10-6 std cc/minute, or 3.33 x 10-7 std cc/s. The permeability is now calculated from the permeation area (12.56 cm2 for the cells I make), from the material thickness, and from the upstream pressure. Typically, one measures the thickness in cm, and the pressure in cm of Hg so that 1 atm is 76cm Hg. The result is that permeability is determined in a unit called barrer. Continuing the example above, if the upstream hydrogen is 15 psig, that’s 2 atmospheres absolute or or 152 cm Hg. Lets say that the material is a polymer of thickness is 0.3 cm; we thus conclude that the permeability is 0.524 x 10-10 scc/cm/s/cm2/cmHg = 0.524 barrer.
This method is capable of measuring permeabilities lower than the previous method, easily lower than 1 barrer, because the results are not fogged by small air leaks or degassing from the membrane material. Leaks of oxygen, and nitrogen show up on the GC output as peaks that are distinct from the permeate peak, hydrogen or whatever you’re studying as a permeate gas. Another plus of this method is that you can measure the permeability of multiple gas species simultaneously, a useful feature when evaluating gas separation polymers. If this type of approach seems attractive, you can build a cell like this yourself, or buy one from us. Send us an email to reb@rebresearch.com, or give us a call at 248-545-0155.
One of the founding ideas of a limited government, as I think our founders intended, is that the power of the state to protect carries with it several dangers. The first of these is cost, all good services and all good protections come at a cost. Generally that is achieved by taxation or by inflation, or by imposing regulations that do more harm than good. Once a tax for a service is accepted the service is really removed, and there is a tendency to over tax or over inflate to maintain it and to mis-distribute the service as well. The people do not become wealthier, or better served, but the people distributing the services win out. There are those who would say we are living through this today.
Another problem with a big, protective government is that the protectors can turn on the people they are supposed to protect. This can be small issues, like firing people who refuse to vaccinate, or large matters like imprisoning enemies. The history of the world is littered with examples of governments taken over by their own police or army. Generally the excuse is that the police is protecting the people from some bigger danger: rioters, disease, subversives. But once the police take over, they are hard to remove. They tend to see anyone who wants to limit their power as another subversive, and they tend to treat treat such people ruthlessly.
In the French Revolution, the group who ran the guillotine was the “committee for public safety”. First they killed to protect the folk from dangerous monarchists, then the clergy, and capitalists, and eventually anyone they considered a threat: That is anyone who considered them a threat. A similar outcome occurred in Russia, the removal of the Tzar lead to a rein of terror by Stalin. Harry Truman wrote saying that the CIA was another Stalinist police force, and wrote that congress was afraid of them. (see his Op-ed here). It seems that FBI director James Comey used made-up evidence of Russian collaboration to try to remove Trump (see NY Post story here).
A final problem with a powerful group of protectors is that it can be bought by outside agents. Rudolf Hess was Truman’s agent for dealing with the UN to promote world peace. It also turns out that he was also a Soviet agent. In Britain in the 50s to 70s, the assistant head of spying, the second in command of MI6, was Kim Philby a Soviet agent. The Soviets helped Philby’s rise by destroying the reputation of anyone who might do the job well. To this day, we regularly find Chinese and Russian agents in our FBI, NSA, and CIA. There is no better place to gather information and spread lies than with the organization that is supposed to protect us.
The title of my essay comes from a satrical poem/ essay written by Juvinal, in first century Rome (read it here). The more famous line is Quis custodiet ipsos custodes? Juvenal points out that not only is group of watchmen/protectors a danger in itself so that, if you hire a watchman to keep your wife chaste, she is likely to stray with the watchman, but he also points out that the watchmen are expensive, and that they are easily bought. Juvenal also points out that cruelty and vanities are common outcomes of a large retinue; if the wife or one of her high eunuchs feels disregarded, everyone lower will be beaten mercilessly. It’s a problem that is best solved, in the home and in politics in general by having a small staff — just what’s really needed. This, I think, was the intent of the founders of our country who limited the number of services provided.
Robert E. Buxbaum, November 27, 2021. As a more-fun way to present watchmen getting excessive, here is a parity song, “Party in the CIA,” by Weird Al. …Better put your hands up and get in the van, Or else you’ll get blown away, Stagin’ a coup like yeah… Party in the CIA.
Platinum catalysts can be very effective at removing hydrogen from air. Platinum promotes the irreversible reaction of hydrogen with oxygen to make water: H2 + 1/2 O2 –> H2O, a reaction that can take off, at great rates, even at temperatures well below freezing. In the 1800s, when platinum was cheap, platinum powder was used to light town-gas, gas street lamps. In those days, street lamps were not fueled by methane, ‘natural gas’, but by ‘town gas’, a mix of hydrogen and carbon monoxide and many impurities like H2S. It was made by reacting coal and steam in a gas plant, and it is a testament to the catalytic power of Pt that it could light this town gas. These impurities are catalytic poisons. When exposed to any catalyst, including platinum, the catalyst looses it’s power to. This is especially true at low temperatures where product water condenses, and this too poisons the catalytic surface.
Nowadays, platinum is expensive and platinum catalysts are no longer made of Pt powder, but rather by coating a thin layer of Pt metal on a high surface area substrate like alumina, ceria, or activated carbon. At higher temperatures, this distribution of Pt improves the reaction rate per gram Pt. Unfortunately, at low temperatures, the substrate seems to be part of the poisoning problem. I think I’ve found a partial way around it though.
My company, REB Research, sells Pt catalysts for hydrogen removal use down to about 0°C, 32°F. For those needing lower temperature hydrogen removal, we offer a palladium-hydrocarbon getter that continues to work down to -30°C and works both in air and in the absence of air. It’s pretty good, but poisons more readily than Pt does when exposed to H2S. For years, I had wanted to develop a version of the platinum catalyst that works well down to -30°C or so, and ideally that worked both in air and without air. I got to do some of this development work during the COVID downtime year.
My current approach is to add a small amount of teflon and other hydrophobic materials. My theory is that normal Pt catalysts form water so readily that the water coats the catalytic surface and substrate pores, choking the catalyst from contact with oxygen or hydrogen. My thought of why our Pd-organic works better than Pt is that it’s part because Pd is a slower water former, and in part because the organic compounds prevent water condensation. If so, teflon + Pt should be more active than uncoated Pt catalyst. And it is so.
where is molar volume. The substance-specific constants and can be understood as an attraction force between molecules and a molecular volume respectively. Alternately, they can be calculated from the critical temperature and pressure as
Now, I’m going to assume that the effect of a hydrophobic surface near the Pt is to reduce the effective value of a. This is to say that water molecules still attract as before, but there are fewer water molecules around. I’ll assume that b remains the same. Thus the ratio of Tc and Pc remains the same but the values drop by a factor of related to the decrease in water density. If we imagine the use of enough teflon to decrease he number of water molecules by 60%, that would be enough to reduce the critical temperature by 60%. That is, from 647 K (374 °C) to 359 K, or -14°C. This might be enough to allow Pt catalysts to be used for H2 removal from the gas within a nuclear wast casket. I’m into nuclear, both because of its clean power density and its space density. As for nuclear waste, you need these caskets.
I’ve begun to test of my theory by making hydrogen removal catalyst that use both platinum and palladium along with unsaturated hydrocarbons. I find it works far better than the palladium-hydrocarbon getter, at least at room temperature. I find it works well even when the catalyst is completely soaked in water, but the real experiments are yet to come — how does this work in the cold. Originally I planned to use a freezer for these tests, but I now have a better method: wait for winter and use God’s giant freezer.
It’s been a while since I did an assessment of hydrogen and batteries for automobile propulsion, and while some basics have not changed, the price and durability of batteries has improved, the price of gasoline has doubled, and the first commercial fuel cell cars have appeared in the USA. The net result (see details below) is that I find the cost of ownership for a gasoline and a battery car is now about the same, depending on usage and location, and that hydrogen, while still more pricey, is close to being a practical option.
EV Chargers. They look so much cooler than gasoline hoses, and the price per mile is about the same.
Lithium battery costs are now about $150/kwh. That’s $10,000 for a 70 kWh battery. That’s about 1/5 the price of a Tesla Model 3. The reliability that Tesla claims is 200,000 miles or more, but that’s with slow charging. For mostly fast charging, Car and Driver’s expectation is 120,000 miles. That’s just about the average life-span of a car these days.
The cost of the battery and possible replacement adds to the cost of the vehicle, but electricity is far cheaper than gasoline, per mile. The price of gasoline has doubled to, currently, $3.50 per gallon. A typical car will get about 24 mpg, and that means a current operation cost of 14.6¢/mile. That’s about $1,460/year for someone who drives 10,000 miles per year. I’ll add about $150 for oil and filter changes, and figure that operating a gas-powered car engine costs about $1,610 per year.
If you charge at home, your electricity costs, on average, 14¢/kWh. This is a bargain compared to gasoline since electricity is made from coal and nuclear, mostly, and is subsidized while gasoline is taxed. At level 2 charging stations, where most people charge, electricity costs about 50¢/kWh. This is three times the cost of home electricity, but it still translates to only about $32 for a fill-up that take 3 hours. According to “Inside EVs”, in moderate temperatures, a Tesla Model 3 uses 14.59 kWh/100 km with range-efficient driving. This translates to 11.7¢ per mile, or $1170/year, assuming 10,000 miles of moderate temperature driving. If you live in moderate climates: Californian, Texas or Florida, an electric car is cheaper to operate than a gasoline car. In cold weather gasoline power still makes sense since a battery-electric car uses battery power for heat, while a gasoline powered car uses waste heat from the engine.
Battery cars are still somewhat of more expensive than the equivalent gasoline car, but not that much. In a sense you can add $400/year for the extra cost of the Tesla above, but that just raises the effective operating cost to about $1,570/year, about the same as for the gasoline car. On the other hand, many folks drive less than 50 miles per day and can charge at home each night. This saves most of the electric cost. In sum, I find that EVs have hit a tipping point, and Tesla lead the way.
Now to consider hydrogen. When most people think hydrogen, they think H2 fuel, and a PEM fuel cell car. The problem here is that hydrogen is expensive, and PEM FCs aren’t particularly efficient. Hydrogen costs about $10/kg at a typical fueling station and, with PEM, that 1 kg of hydrogen takes you only about 25 miles. The net result is that the combination hydrogen + PEM results in a driving cost of about 40¢/mile, or about three times the price of gasoline. But Toyota has proposed two better options. The fist is a PEM hybrid, the hydrogen Prius. It’s for the commuter who drives less than about 40 miles per day. It has a 10kWh battery, far cheaper than the Tesla above, but enough for the daily commute. He or she would use charge at home at night, and use hydrogen fuel only when going on longer trips. If there are few long trips, you come out way ahead.
Toyota 2021 Mirai, hydrogen powered vehicle
Toyota also claims to have a hydrogen powered Corolla or debut in 2023. This car will have a standard engine, and I would expect (hope) will drive also — preferably — on hythane, a mix of hydrogen and methane. Hythane is much cheaper per volume, and more energy dense, see my analysis. While Toyota has not said that their Corolla would run on hythane, it is supposed to have an internal combustion engine, and that suggests that hythane will work in it.
A more advanced option for Toyota or any other car/truck manufacturer would be to design to use solid oxide fuel cells, SOFCs, either with hydrogen or hythane. SOFCs are significantly more efficient than PEM, and they are capable of burning hythane, and to some extent natural gas too. Hythane is not particularly available, but it could be. Any station that currently sells natural gas could sell hythane. As for delivery to the station, natural gas lines already exist underground, and the station would just blend in hydrogen, produced at the station by electrolysis, or delivered. Hythane can also be made locally from sewer gas methane, and wind-power hydrogen. Yet another SOFC option is to start with natural gas and convert some of the natural gas to hydrogen on-board using left-over heat from the SOFC. I’ve a patent for this process.
Speaking of supply network, I should mention the brown outs we’ve been having in Detroit. Electric cars are part of the stress to the electric grid, but I believe that, with intelligent charging (and discharging) the concern is more than manageable. The driver who goes 10,000 miles per year only adds about 2,350 kWh/year of extra electric demand. This is a small fraction of the demand of a typical home, 12,154 kWh/year.It’s manageable. Then again, hythane adds no demand to the electric grid and the charge time is quicker — virtually instantaneous.
is 
and 
can be understood as an attraction force between molecules and a molecular volume respectively. Alternately, they can be calculated from the 
