Category Archives: REB Research products

How I size heat exchangers

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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:

WHX = flow (mols/second)*heat capacity per mol (J/°C – mol)* ∆Tin-out (350°C).

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.

Robert Buxbaum June 3, 2024

Deadly screw sizes, avoid odd numbers and UNF.

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The glory of American screws and bolts is their low cost ubiquity, especially in our coarse thread (UNC = United National Coarse) sizes. Between 1/4 inch and 5/8″, they are sized in 1/16″ steps, and after that in 1/8″ steps. Below 3/16″, they are sized by wire gauges, and generally they have unique pitch sizes. All US screws and bolts are measured by their diameter and threads per inch. Thus, the 3/8-16 (UNC) has an outer diameter (major diameter) of 3/8″ with 16 threads per inch (tpi). 16 tpi is an ideal thread number for overall hold strength. No other bolt has 16 threads per inch so it is impossible to use the wrong bolt in a hole tapped for 3/8-16. The same is true for basically every course thread with a very few exceptions, mainly found between 3/16″ and 1/4″ where the wire gauges transition to fractional sizes. Because of this, if you stick to UTC you are unlikely to screw up, as it were. You are also less-likely to cross-thread.

I own one of these. It’s a tread pitch gauge.

US fine threads come in a variety of standards, most notably UNF = United National Fine. No version of fine thread is as strong as coarse because while there are more threads per inch, each root is considerably weaker. The advantage of fine treads is for use with very thin material, or where vibration is a serious concern. The problem is that screwups are far more likely and this diminishes the strength even further. Consider the 7/16″ – 24 (UNF). This bolt will fit into a nut or flange tapped for 1/2″- 24. The fit will be a little loose, but you might not notice. You will be able to wrench it down so everything looks solid, but only the ends of the threads are holding. This is a accident waiting to happen. To prevent such mistakes you can try to never allow a 7/6″-24 bolt into your shop, but this is uncomfortably difficult. If you ever let a 7/6″-24 bolt in, some day someone will grab it and use it, in all likelihood with a 1/2″ -24 nut or flange, since these are super-common. Under stress, the connection will fail in the worst possible moment.

Other UNF bolts and nuts present the same screwup risk. For example, between the 3/8″-24 and 5/16″-24 (UNF), or the #10-32 (UNF) and also with the 3/16″- 32, and the latter with the #8-32 (UNC). There is also a French metric with 0.9mm — this turns out to be identical to -32 pitch. The problem appears with any bolt pair where with identical pitch and the major diameter of the smaller bolt has a larger outer diameter (major diameter) than the inner diameter (minor diameter) of the larger bolt. If these are matched, the bolts will seem to hold when tightened, but they will fail in use. You well sometimes have to use these sizes because they match with some purchased flange. If you have to use them, be careful to use the largest bolt diameter that will fit into the threaded hole.

Where I have the option, my preference is to stick to UNC as much as possible, even where vibration is an issue. In vibration situations, I prefer to add a lock nut or sometimes, an anti-vibration glue, locktite, available in different release temperatures. Locktite is also helpful to prevent gas leaks. In our hydrogen purifiers, I use lock washers on the ground connection from the power cord, for example.

I try to avoid metric, by the way. They less readily available in the US, and more expensive. The other problem with metric is that there are two varieties (Standard and French — God love the French engineering) and there are so many sizes and pitches that screwups are common. Metric bolts come in every mm diameter, and often fractional mm too. There is a 2mm, a 2.3mm, a 2.5mm, and a 2.6mm, often with overlapping pitches. The pitch of metric screws and bolts is measured by their spacing, by the way, so a 1mm metric pitch means there is 1mm between threads, the the equivalent of a 24.5 pitch in the US, and a 0.9mm pitch = US-32. Thread confusion possibilities are endless. A M6x1 (6mm OD x 1mm pitch) is easily confused with a M5x1 or a M7x1, and the latter with the M7.5×1. A M8x1.25 is easily confused with a M9x1.25, and a M14x2 with an M16x2. And then there is confusion with US bolts: a 2.5mm metric pitch is nearly identical to a US 10tpi pitch. I can not rid myself of US threads, so I avoid metric where I can. As above, problems arise if you use a smaller diameter bolt in a larger diameter nut.

For those who have to use metric, I suggest you always use the largest bolt that will fit (assuming you can find it). I try to avoid bringing odd-size bolts into their shop, that is, stick to M6, M8, M10. It’s not always possible, but it’s a suggestion. I get equipment with odd-size metric bolts too. My preference is to stick to UNC and to avoid odd numbers.

Robert Buxbaum, January 23, 2024. Note: I’ve only really discussed bolt sizes between about #4 and 1″, and I didn’t consider UNRC or UNJF or other, odd options. You can figure these issues out yourself from the above, I think.

Use iodine against Bad breath, Bad beer, Flu, RSV, COVID, monkeypox….

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We’re surrounded by undesired bacteria, molds, and viruses. Some are annoying, making our feet smell, our teeth rot, and our wine sour. Others are killers, particularly for the middle aged and older. Despite little evidence, the US government keeps pushing masks and inoculations with semi-active vaccine that does nothing to stop the spread. Among the few things one can do to stop the spread of disease, and protect yourself, is to kill the bacteria, molds and viruses with iodine. Iodine is cheap, effective even at very low doses, 0.1% to 10 parts per million, and it lasts a lot longer than alcohol. Dilute iodine will not dye your skin, and it does not sting. A gargle of iodine will kill COVID and other germs (e.g. thrush) and it has even been shown to be a protective, stopping COVID 19 and flu even if used before exposure. On a more practical level. I also use it to cleanse my barrels before making beer — It’s cheaper than the Camden they sell in stores.

Iodine is effective when used on surfaces, and most viruses spread by surfaces. A sick person coughs. Droplets end up on door knobs, counters, or in your throat, leaving virus particles that do not die in air. You touch the surface, and transfer the virus to your eyes and nose. Here’s a video I made. A mask doesn’t help because you rub your eyes around the mask. But iodine kills the virus on the surface, and on your hands, and lasts there far longer than alcohol does. Vaccines always come with side-effects, but there are no negative side effects to sanitization with dilute iodine. Here is a video I did some years ago on the chemistry of iodine.

Robert Buxbaum, February 1, 2023. I don’t mean to say that all bacteria and fungi are bad, it’s just that most of them are smelly. Even the good ones that give us yogurt, beer, blue cheese, and sour kraut tend to be smelly. They have the annoying tendency to causing your wine to taste and smell like sour kraut or cheese, and they cause your breath and feet to smell the same. If you’re local, I’ll give you some free iodine solution. Otherwise, you’ll have to buy it through REB Research.

Hydrogen transport in metallic membranes

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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.

Robert Buxbaum, January 22, 2023

A simpler way to recycle the waste fuel of a SOFC.

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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.

Robert Buxbaum, December 8, 2022.

My home-made brandy and still.

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MY home-made still, and messy lab. Note the masking tape seal and the nylon hoses. Nylon is cheaper than copper. The yellow item behind the burner is the cooling water circulation pump. The wire at top and left is the thermocouple.

I have an apple tree, a peach tree, and some grape vines. They’re not big trees, but they give too much fruit to eat. The squirrels get some, and we give some away. As for the rest, I began making wine and apple jack a few years back, but there’s still more fruit than I can use. Being a chemical engineer, I decided to make brandy this year, so far only with pears and apples.

The first steps were the simplest: I collected fruit in a 5 gallon, Ace bucket, and mashed it using a 2×4. I then added some sugar and water and some yeast and let it sit with a cover for a week or two. Bread yeast worked fine for this, and gives a warm flavor, IMHO. A week or so later, I put the mush into a press I had fro grapes, shown below, and extracted the fermented juice. I used a cheesecloth bag with one squeezing, no bag with the other. The bag helped, making cleanup easier.

The fruit press, used to extract liquid. A cheese cloth bag helps.

I did a second fermentation with both batches of fermented mash. This was done in a pot over a hot-plate on warm. I added more sugar and some more yeast and let it ferment for a few more days at about 78°F. To avoid bad yeasts, I washed out the pot and the ace bucket with dilute iodine before using them– I have lots of dilute iodine around from the COVID years. The product went into the aluminum “corn-cooker” shown above, 5 or 6 gallon size, that serves as the still boiler. The aluminum cover of the pot was drilled with a 1″ hole; I then screwed in a 10″ length of 3/4″ galvanized pipe, added a reducing elbow, and screwed that into a flat-plate heat exchanger, shown below. The heat exchanger serves as the condenser, while the 3/4″ pipe is like the cap on a moonshiner still. Its purpose is to keep the foam and splatter from getting in the condenser.

I put the pot on the propane burner stand shown, sealed the lid with masking tape (it worked better than duct tape), hooked up the heat exchanger to a water flow, and started cooking. If you don’t feel like making a still this way, you can buy one at Home Depot for about $150. Whatever route you go, get a good heat exchanger/ condenser. The one on the Home-depot still looks awful. You need to be able to take heat out as fast as the fire puts heat in, and you’ll need minimal pressure drop or the lid won’t seal. The Home Depot still has too little area and too much back-pressure, IMHO. Also, get a good thermometer and put it in the head-space of the pot. I used a thermocouple. Temperature is the only reasonable way to keep track of the progress and avoid toxic distillate.

A flat-plate heat exchanger, used as a condenser.

The extra weight of the heat exchanger and pipe helps hold the lid down, by the way, but it would not be enough if there was a lot of back pressure in the heat exchanger-condenser. If your lid doesn’t seal, you’ll lose your product. If you have problems, get a better heat exchanger. I made sure that the distillate flows down as it condenses. Up-flow adds back pressure and reduces condenser efficiency. I cooled the condenser with water circulated to a bucket with the cooling water flowing up, counter current to the distillate flow. I could have used tap water via a hose with proper fittings for cooling, but was afraid of major leaks all over the floor.

With the system shown, and the propane on high, it took about 20 minutes to raise the temperature to near boiling. To avoid splatter, I turned down the heater as the temperature approached 150°F. The first distillate came out at 165°F, a temperature that indicated it was not alcohol or anything you’d want to drink. I threw away the first 2-3 oz of this product. You can sniff or sip a tiny amount to convince yourself that this this is really nasty, acetone, I suspect, plus ethyl acetate, and maybe some ether and methanol. Throw it away!

After the first 2-3 ounces, I collected everything to 211°F. Product started coming in earnest at about 172°F. I ended distillation at 211°F when I’d collected nearly 3 quarts. For my first run, my electronic thermometer was off and I stopped too early — you need a good thermometer. The material I collected and was OK in taste, especially when diluted a bit. To test the strength, I set some on fire, the classic “100% proof test”, and diluted till it to about 70% beyond. This is 70% proof, by the classic method. I also tried a refractometer, comparing the results to whiskey. I was aiming for 60-80 proof (30-40%).

My 1 gallon aging barrel.

I tried distilling a second time to improve the flavor. The result was stronger, but much worse tasting with a loss of fruit flavor. By contrast, a much better resulted from putting some distillate (one pass) in an oak barrel we had used for wine. Just one day in the barrel helped a lot. I’ve also seen success putting charred wood cubes set into a glass bottle of distillate. Note: my barrel, as purchased, had leaks. I sealed them with wood glue before use.

I only looked up distilling law after my runs. It varies state to state. In Michigan, making spirits for consumption, either 1 gal or 60,000 gal/year, requires a “Distilling, Rectifying, Blending and/or Bottling Spirits” Permit, from the ATF Tax and Trade Bureau (“TTB”) plus a Small Distiller license from Michigan. Based on the sale of stills at Home Depot and a call to the ATF, it appears there is little interest in pursuing home distillers who do not sell, despite the activity being illegal. This appears similar to state of affairs with personal use marijuana growers in the state. Your state’s laws may be different, and your revenuers may be more enthusiastic. If you decide to distill, here’s some music, the Dukes of Hazard theme song.

Robert Buxbaum, November 23, 2022.

A more accurate permeation tester

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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.

Robert Buxbaum, April 27, 2022.

Low temperature hydrogen removal

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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.

Think of this in terms of the  Van der Waals equation of state:{\displaystyle \left(p+{\frac {a}{V_{m}^{2}}}\right)\left(V_{m}-b\right)=RT}

where V_{m} is molar volume. The substance-specific constants a and b 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

{\displaystyle a={\frac {27(RT_{c})^{2}}{64p_{c}}}}{\displaystyle b={\frac {RT_{c}}{8p_{c}}}.}

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.

Robert E. Buxbaum October 20, 2021. I did a fuller treatment of the thermo above, a few weeks back.

Weird thermodynamics near surfaces can prevent condensation and make water more slippery.

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It is a fundamental of science that that the properties of every pure one-phase material is totally fixed properties at any given temperature and pressure. Thus for example, water at 0°C is accepted to always have a density of 0.998 gm/cc, a vapor pressure of 17.5 Torr, a viscosity of 1.002 centipoise (milliPascal seconds) and a speed of sound of 1481 m/s. Set the temperature and pressure of any other material and every other quality is set. But things go screwy near surfaces, and this is particularly true for water where the hydrogen bond — a quantum bond — predominates.

its vapor pressure rises and it becomes less inclined to condense or freeze. I use this odd aspect of thermodynamics to keep my platinum-based hydrogen getter catalysis active at low temperatures where they would normally clog. Normal platinum catalysts are not suitable for hydrogen removal at normal temperatures, eg room temperature, because the water that forms from hydrogen oxidation chokes off the catalytic surface. Hydrophobic additions prevent this, and I’d like to show you why this works, and why other odd things happen, based on an approximation called the  Van der Waals equation of state:

{\displaystyle \left(p+{\frac {a}{V_{m}^{2}}}\right)\left(V_{m}-b\right)=RT} (1)

This equation described the molar volume of a pure material, V_{m}, of any pure material based not the pressure, the absolute temperature (Kelvin) and two, substance-specific constants, a and b. These constants can be understood as an attraction force term, and a molecular volume respectively. It is common to calculate a and b from the critical temperature and pressure as follows, where Tc is absolute temperature:

{\displaystyle a={\frac {27(RT_{c})^{2}}{64p_{c}}}}, {\displaystyle b={\frac {RT_{c}}{8p_{c}}}.} (2 a,b)

For water Tc = 647 K (374°C) and 220.5 bar. Plugging in these numbers, the Van der Waals gives reasonable values for the density of water both as a liquid and a gas, and thus gives a reasonable value for the boiling point.

Now consider the effect that an inert surface would have on the effective values of a and b near that surface. The volume of the molecules will not change, and thus b will not change, but the value of a will change, likely by about half. This is because, the number of molecules surrounding any other molecule is reduced by about half while the inert surface adds nothing to the attraction. Near a surface, surrounding molecules still attract each other the same as before, but there are about half as many molecules at any temperature and pressure.

To get a physical sense of what the surface does, consider using the new values of a and b to determine a new value for Tc and Pc, for materials near the surface. Since b does not change, we see that the presence of a surface does not affect the ratio of Tc and Pc, but it decreases the effective value of Tc — by about half. For water, that is a change from 647 K to 323.5K, 50.5°C, very close to room temperature. Pc changes to 110 bar, about 1600 psi. Since the new value of Tc is close to room temperature, the the density of water will be much lower near the surface, and the viscosity can be expected to drop. The net result is that water flows more readily through a teflon pipe than through an ordinary pipe, a difference that is particularly apparent at small diameters.

This decrease in effective Tc is useful for fire hoses, and for making sailing ships go faster (use teflon paint) and for making my hydrogen removal catalysts more active at low temperatures. Condensed water can block the pores to the catalyst; teflon can forestall this condensation. It’s a general trick of thermodynamics, reasonably useful. Now you know it, and now you know why it works.

Robert Buxbaum August 30, 2021

Alice’s Restaurant and Nuclear Waste

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It’s not uncommon for scientists to get inspiration from popular music. I’d already written about how the song ‘City of New Orleans’ inspires my view of the economics of trains, I’d now like to talk about dealing with nuclear waste, and how the song Alice’s Restaurant affects my outlook.

As I see it, nuclear power is the elephant in the room in terms of clean energy. A piece of uranium the size of a pencil eraser produces as much usable energy as three rail cars of coal. There is no air pollution and the land use is far less than for solar or wind power. The one major problem was what to do with the left over eraser-worth of waste. Here’s the song, it’s 18 1/2 minutes long. The key insight appeared in the sixth stanza: “…at the bottom of the cliff there was another pile of garbage. And we decided that one big pile Is better than two little piles…”

The best way to get rid of nuclear waste would be (as I’ve blogged) to use a fast nuclear reactor to turn the worst components into more energy and less-dangerous elements. Unfortunately doing this requires reprocessing, and reprocessing was banned by Jimmy Carter, one of my least favorite presidents. The alternative is to store the nuclear waste indefinitely, waiting for someone to come up with a solution, like allowing it to be buried in Yucca Mountain, the US burial site that was approved, but that Obama decided should not be used. What then? We have nuclear waste scattered around the country, waiting. I was brought in as part of a think-tank, to decide what to do with it, and came to agree with several others, and with Arlo Guthrie, that one big pile [of waste] Is better than two little piles. Even if we can’t bury it, it would be better to put the waste in fewer places (other countries bury their waste, BTW).

That was many years ago, but even the shipping of waste has been held up as being political. Part of the problem is that nuclear waste gives off hydrogen — the radiation knocks hydrogen atoms off of water, paper, etc. and you need to keep the hydrogen levels low to be able to transport the waste safely. As it turns out we are one a few companies that makes hydrogen removal pellets and catalysts. Our products have found customers running tourist submarines (lead batteries also give off hydrogen) and customers making sealed electronics, and we are waiting for the nuclear shipping industry to open up. In recent months, I’ve been working on improving our products so they work better at low temperature. Perhaps I’ll write about that later, but here’s where you’d go to buy our current products.

Robert Buxbaum, July 4, 2021. I’ve done a few hydrogen-related posts in a row now. In part that’s because I’d noticed that I went a year or two talking history and politics, and barely talking about H2. I know a lot about hydrogen — that’s my business– as for history or politics, who knows.