Tag Archives: purifier

Getter purifiers versus Membrane purifiers

There are two main types of purifiers used for gases: getters and membranes. Both can work for you in almost any application, and we make both types at REB Research – for hydrogen purification mostly, but sometimes for other applications. The point of this essay is which one makes more sense for which application. I’ll mostly talk about hydrogen purification, but many of the principles apply generally. The way both methods work is by separating the fast gas from the slower gas. With most getters and most membranes, hydrogen is the fast gas. That is to say, hydrogen usually is the component that goes through the membrane preferentially, and hydrogen is the gas that goes through most getters preferentially. It’s not always the case, but generally.

Scematic of our getter beds for use with inert gasses. There are two chambers; one at high temperature to remove water, nitrogen, methane, CO2, and one at lower temperature the remove H2. The lower temperature bed can be regenerated.

Our getter beds for use with inert gasses have two chambers; one is high temperature to remove water, nitrogen, etc. and one at lower temperature the remove H2. The lower temperature bed can be regenerated.

Consider the problem of removing water and similar impurities from a low-flow stream of helium for a gas chromatograph. You probably want to use a getter because there are not really good membranes that differentiate helium from impurities. And even with hydrogen, at low flow rates the getter system will probably be cheaper. Besides, the purified gas from a getter leaves at the same pressure as it entered. With membranes, the fas gas (hydrogen) leaves at a lower pressure. The pressure difference is what drives membrane extraction. For inert gas drying our getters use vanadium-titanium to absorb most of the impurities, and we offer a second, lower temperature bed to remove hydrogen. For hydrogen purification with a bed, we use vanadium and skip the second bed. Other popular companies use other getters, e.g. drierite or sodium-lead. Whatever the getter, the gas will leave purified until the getter is used up. The advantage of sodium lead is that it gets more of the impurity (Purifies to higher purity). Vanadium-titanium removes not only water, but also oxygen, nitrogen, H2S, chlorine, etc. The problem is that it is more expensive, and it must operate at warm (or hot) temperatures. Also, it does not removed inert gases, like helium or argon from hydrogen; no getter does.

To see why getters can be cheaper than membranes if you don’t purify much gas, or if the gas starts out quite pure, consider a getter bed that contains 50 grams of vanadium-titanium (one mol). This amount of getter will purify 100 mols of fast gas (hydrogen or argon, say) if the fast gas contains 1% water. The same purifier will purify 1000 mols of fast gas with 0.1% impurity. Lets say you plan to use 1 liter per minute of gas at one atmosphere and room temperature, and you start with gas containing 0.1% impurity (3N = 99.9% gas). Since the volume of 100 mols of most gases a these conditions is 2400 liters. Thus, you can expect our purifier to last for 400 hours (two weeks) at this flow rate, or for four years if you start with 99.999% gas (5N). People who use a single gas chromatograph or two, generally find that getter-based purifiers make sense; they typically use only about 0.1 liters/minute, and can thus get 4+ years’ operation even with 4N gas. If you have high flows, e.g. many chromatographs or your gas is less-pure, you’re probably better off with a membrane-based purifier, shown below. That what I’ll discuss next.

Our membrane reactors and most of our hydrogen purifiers operate with pallium-membranes and pressure-outside. Only hydrogen permeates through the palladium membrane.

Our membrane reactors and most of our hydrogen purifiers operate with pallium-membranes and pressure-outside. Only hydrogen permeates through the palladium membrane.

The majority of membrane-based purifiers produced by our company use metallic membranes, usually palladium alloys, and very often (not always) with pressure on the outside. Only hydrogen passes through the membranes. Even with very impure feed gases, these purifiers will output 99.99999+% pure H2 and since the membrane is not used up, they will typically operate forever so long as there is no other issue — power outages can cause problems (we provide solutions to this). The main customers for our metallic membrane purifiers are small laboratories use and light manufacturers. We also manufacture devices that combine a reformer that makes 50% pure hydrogen from methanol + steam where the membranes are incorporated with the reactor — a membrane reformer, and this has significant advantages. There is no equivalent getter-based device, to my knowledge because it would take too much getter to deal with such impure gas.

Metal membranes are impermeable to inert gases like helium and argon too, and this is an advantage for some customers, those who don’t want anything but hydrogen. For other customers, those who want a cheaper solution, or are trying to purify large amounts of helium, we provide polymeric membranes, a lower cost, lower temperature option. Metal membranes are also used with deuterium or tritium, the higher isotopes of hydrogen. The lighter isotopes of hydrogen permeate these membranes faster than the heavier ones for reasons I discuss here.

Robert Buxbaum, August 26, 2018

Purifying the Hydrogen from Browns gas, HHO, etc.

Perhaps the simplest way to make hydrogen is to stick two electrodes into water and to apply electricity. The gas that is produced is mostly hydrogen, and is sometimes suitable for welding or for addition to an automobile engine to increase the mileage. Depending on the electrodes and whether salt is added to the water, the gas that is produced can be Browns gas, HHO,  town gas, or some relative of the three. We are sometimes asked if we can purify the product of this electrolysis, and my answer is typically: “maybe,” or “it depends.”

If the electrode was made of stainless steel and the water contained only KOH or baking soda, the gas that results will be mostly hydrogen and you will be able to purify it somewhat with a polymer membrane if you wish. The gas isn’t very explosive generally, since most of the oxygen that results from the electrolysis will go into rusting out the electrodes. The reaction is thus, H2O + Fe –> H2 + FeO. To see if this is what you’ve got, you can use determine the ratio of gas production with a simple version of the Hoffman apparatus made from (for example) two overturned glass jars, or by separating the electrodes with a paper towel. You can also determine the H2 to O2 ratio (if you know a bit more physics) from a measure of the amperage and the rate of gas production. The hydrogen you form with steel plates will always contain some oxygen though, as well as some nitrogen and water vapor. While a polymer membrane will remove most of the oxygen and nitrogen in this gas, it won’t remove all, and it will not generally remove any of the water. With this gas, I suspect that you would be better off just using it as it is. This is particularly so if the fraction of oxygen is more than a few percent: hydrogen with more oxygen than this becomes quite explosive.

Since this gas will contain water, you probably don’t want to store it, and you probably don’t want to purify it over a metal, either, There are two reasons for this: the water can condense out during storage, and will tend to rust whatever metal it contacts (it’s often alkaline). What’s more, the small amount of oxygen in the hydrogen is likely to react over a hydrogen storage metal to form water and heat. This may give rise to the explosion you were trying to avoid. This is clearly the quick a dirty approach to making hydrogen.

Another version of electrolysis gas, one that’s even quicker and dirtier than the above involves the use of table salt instead of KOH or baking soda. The hydrogen that results will contain chlorine as an impurity, and will be quite toxic, but it will be somewhat less explosive.The hydrogen will smell like bleach and the water you use will turn slightly greenish and quite alkaline. Both the liquid and gas are definitely bad news unless your aim was to make chlorine and alkali; this is called the chlor-alkali process for a reason. On a personal note, as a 12 year old I tried this and was confused about why I got equal volumes of gas on the cathode and anode. The reason was that I was making Cl2, and not O2: the chemistry is 2 H2O + 2 NaCl –> H2 + Cl2 + 2 NaOH. I then I used the bromide version reaction to make a nice sample of bromine liquid. That is, I used KBr instead of table salt. Bromine is brown, oily, and only sparingly soluble in water.

Another version of this electrolysis process involves the use of graphite electrodes. If you are lucky, this will give you a mix of CO and hydrogen and not H2 and O2. This mix is a called “town gas.” It’s a very good welding gas since it is not explosive. It is, however, quite toxic. If you begin to get a headache using this gas stop immediately: you’re experiencing CO poisoning. The reaction here is H2O + C –> H2 + CO. CO headaches just get worse and worse until you die. If you are not lucky here you can get HHO instead of town gas, and this is quite explosive: H2O –> H2 + 1/2 O2. The volume ratio will be a key clue as to which you are making; another clue is to put a small volume in a paper bag and light it. If the bag explodes with a terrific bang, you’ve made the wrong gas. Stop!

With all of these gases I would recommend that you add a polymer of paper membrane in the water between the electrodes. Filter paper will work fine for this as will ceramic paper; the classic membrane for this was asbestos. If you keep the two product gas streams separate as soon as they are formed, you’ll avoid most of your explosion-safety issues. Few people take this advice, I’ve found; they think there must be some simpler way. Trust me: this is the classic, safe way to make electrolysis hydrogen.

A balloon filled with pure hydrogen will not ignite. To show you, here is a 2.5 min long video where I poke a lit cigar into a mylar balloon filled with hydrogen from my membrane reactor generators. Note that this hydrogen does not even burn in the balloon because it is oxygen free. As a safety check try this with your hydrogen, but only on a much-smaller scale. Pure hydrogen will not go boom, impure hydrogen will. My advice: keep safe and healthy. You’ll feel better that way, and your heirs will be less inclined to sue me.

In case you are wondering how electrolysis hydrogen can add to the gas mileage, the simple answer is that it increases the combustion speed and the water vapor decreases the parasitic loss due to vacuum. I’ve got some more information on this here. I hope this advice helps with your car project or any other electrolysis option. In my opinion, one should use a membrane in the water to separate the components at formation in all but the smallest experiments and with the smallest amperage sources. Even these should be done only in a well-ventilated room or on a car that is parked outside of the house. Many of the great chemists of the 1800s died doing experiments like these; learn from their mistakes and stay among the living.

Big new hydrogen purifier ships

We shipped out our largest hydrogen purifier to date on Thursday, one designed for use in hydrogen-powered airplanes. I’m pretty happy; lots of throughput, light weight, low pressure drop, quite durable. We had a pizza party Friday to celebrate(if we didn’t invite you, sorry). I’m already working on design improvements (lessons learned) in case we get another order, or another, similar customer. I think we could do even better in our next version.

Largest hydrogen purifier to date pressure test

Here is our latest hydrogen purifier to date being pressure tested. Output is 650 slpm; that’s 40 m3/hr, 3.5 kg/hr. The device is tied down for burst-pressure testing behind a blast fort, just in case the thing bursts during tests. So far, no failures, no leaks. I sure hope the customer pays.

here's our largest H2 purifier being burst-pressure tested

here’s our largest H2 purifier being burst-pressure tested