Tag Archives: oxygen

Brown’s gas for small scale oxygen production.

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Some years ago I wrote a largely negative review of Brown’s gas, but the COVID crisis in India makes me want to reconsider. Browns gas can provide a simple source of oxygen for those who are in need. First, an explanation, Browns gas is a two-to-one mix of hydrogen and oxygen; it’s what you get when you do electrolysis of water without any internal separator. Any source of DC electricity will do, e.g. the alternator of a car or a trickle charger of the sort folks buy for their car batteries, and almost any electrode will do too (I’d suggest stainless steel). You can generate pressure just by restricting flow from the electrolysis vessel, and it can be a reasonable source of small-scale oxygen or hydrogen. The reaction is:

H2O –> H2 + 1/2 O2.

The problem with Brown’s gas is that it is explosive, more explosive than hydrogen itself, so you have to handle it with care; avoid sparks until you separate the H2 from the O2. Even the unseparated mix has found some uses, e.g. as a welding gas, or for putting in cars to avoid misfires, increase milage, and decrease pollution. I think that methanol reforming is a better source of automotive hydrogen: hydrogen is a lot safer than this hydrogen-oxygen mix.

Browns gas to oxygen for those who need it.

The mix is a lot less dangerous if you separate the oxygen from the hydrogen with a membrane, as I show in the figure. at right. If you do this it’s a reasonable wy to make oxygen for patients who need oxygen. The electrolysis cell can be a sealed bottle with water and the electrodes; add a flow restriction as shown to create the hydrogen pressure that drives the separation. The power can be an automotive trickle charger. You can get this sort of membranes from REB Research, here and many other suppliers. REB provide consulting services if you like.

In a pinch, you don’t even need the membrane, by the way. You can rely on your lungs to make the separation. A warning, though, the mix is dangerous. Avoid all sparks. Also, don’t put salt into the water. You can can put in some baking soda or lye to speed the electrolysis, but If you put salt in, you’ll find you don’t make oxygen, but will instead make chlorine. And chlorine is deadly. If you’re not sure, smell the gas. If it smells acrid, don’t use it. This is the chlorine-forming reaction.

2NaCl + 2 H2O –> H2 + Cl2 + 2NaOH

Ideally you should vent the hydrogen stream out the window, but for short term, emergency use, the hydrogen can be vented into your home. Don’t do this if anyone smokes (not that anyone should smoke about someone on oxygen). This is a semi-patentable design, but I’m giving it away; not everything that can be patented should be.

Robert Buxbaum, May 13, 2021.

magnetic separation of air

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As some of you will know, oxygen is paramagnetic, attracted slightly by a magnet. Oxygen’s paramagnetism is due to the two unpaired electrons in every O2 molecule. Oxygen has a triple-bond structure as discussed here (much of the chemistry you were taught is wrong). Virtually every other common gas is diamagnetic, repelled by a magnet. These include nitrogen, water, CO2, and argon — all diamagnetic. As a result, you can do a reasonable job of extracting oxygen from air by the use of a magnet. This is awfully cool, and could make for a good science fair project, if anyone is of a mind.

But first some math, or physics, if you like. To a good approximation the magnetization of a material, M = CH/T where M is magnetization, H is magnetic field strength, C is the Curie constant for the material, and T is absolute temperature.

Ignoring for now, the difference between entropy and internal energy, but thinking only in terms of work derived by lowering a magnet towards a volume of gas, we can say that the work extracted, and thus the decrease in energy of the magnetic gas is ∫∫HdM  = MH/2. At constant temperature and pressure, we can say ∆G = -CH2/2T.

The maximum magnetization you’re likely to get with any permanent magnet (not achieved to date) is about 50 Tesla, or 40,000 ampere meters. At 20°C, the per-mol, magnetic susceptibility of oxygen is 1.34×10−6  This suggests that the Curie constant is 1.34 ×10−6 x 293 = 3.93 ×10−4. Applying this value to oxygen in a 50 Tesla magnet at 20°C, we find the energy difference, ∆G is 1072 J/mole = RT ln ß where ß is a concentration ratio factor between the O2 content of the magnetized and un-magnetized gas, C1/C2 =ß

At room temperature, 298K ß = 1.6, and thus we find that the maximum oxygen concentration you’re likely to get is about 1.6 x 21% = 33%. It’s slightly more than this due to nitrogen’s diamagnetism, but this effect is too small the matter. What does matter is that 33% O2 is a good amount for a variety of medical uses.

I show below my simple design for a magnetic O2 concentrator. The dotted line is a permeable membrane of no selectivity – with a little O2 permeability the design will work better. All you need is a blower or pump. A coffee filter could serve as a membrane.bux magneitc air separator

This design is as simple as the standard membrane-based O2 concentrator – those based on semi-permeable membranes, but this design should require less pressure differential — just enough to overcome the magnet. Less pressure means the blower should be smaller, and less noisy, with less energy use.  I figure this could be really convenient for people who need portable oxygen. With current magnets it would take 4-5 stages or low temperatures to reach this concentration, still this design could have commercial use, I’d think.

On the theoretical end, an interesting thing I find concerns the effect on the entropy of the magnetic oxygen. (Please ignore this paragraph if you have not learned statistical thermodynamics.) While you might imagine that magnetization decreases entropy, other-things being equal because the molecules are somewhat aligned with the field, temperature and pressure being fixed, I’ve come to realize that entropy is likely higher. A sea of semi-aligned molecules will have a slightly higher heat capacity than nonaligned molecules because the vibrational Cp is higher, other things being equal. Thus, unless I’m wrong, the temperature of the gas will be slightly lower in the magnetic area than in the non-magnetic field area. Temperature and pressure are not the same within the separator as out, by the way; the blower is something of a compressor, though a much less-energy intense one than used for most air separators. Because of the blower, both the magnetic and the non magnetic air will be slightly warmer than in the surround (blower Work = ∆T/Cp). This heat will be mostly lost when the gas leaves the system, that is when it flows to lower pressure, both gas streams will be, essentially at room temperature. Again, this is not the case with the classic membrane-based oxygen concentrators — there the nitrogen-rich stream is notably warm.

Robert E. Buxbaum, October 11, 2017. I find thermodynamics wonderful, both as science and as an analog for society.

The chemistry of sewage treatment

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The first thing to know about sewage is that it’s mostly water and only about 250 ppm solids. That is, if you boiled down a pot of sewage, only about 1/40 of 1% of it would remain as solids at the bottom of the pot. There would be some dried poop, some bits of lint and soap, the remains of potato peelings… Mostly, the sewage is water, and mostly it would have boiled away. The second thing to know, is that the solids, the bio-solids, are a lot like soil but better: more valuable, brown gold if used right. While our county mostly burns and landfills the solids remnant of our treated sewage, the wiser choice would be to convert it to fertilizer. Here is a comparison between the composition of soil and bio-solids.

The composition of soil and the composition of bio-solid waste. biosolids are like soil, just better.

The composition of soil and the composition of bio-solid waste. biosolids are like soil, just better.

Most of Oakland’s sewage goes to Detroit where they mostly dry and burn it, and land fill the rest. These processes are expensive and engineering- problematic. It takes a lot of energy to dry these solids to the point where they burn (they’re like really wet wood), and even then they don’t burn nicely. As shown above, the biosolids contain lots of sulfur and that makes combustion smelly. They also contain nitrate, and that makes combustion dangerous. It’s sort of like burning natural gun powder.

The preferred solution is partial combustion (oxidation) at room temperature by bacteria followed by conversion to fertilizer. In Detroit we do this first stage of treatment, the slow partial combustion by bacteria. Consider glucose, a typical carbohydrate,

-HCOH- + O2 –> CO2 + H2O.    ∆G°= -114.6 kcal/mol.

The value of ∆G°, is relevant as a determinate of whether the reaction will proceed. A negative value of ∆G°, as above, indicates that the reaction can progress substantially to completion at standard conditions of 25°C and 1 atm pressure. In a sewage plant, many different carbohydrates are treated by many different bacteria (amoebae, paramnesia, and lactobacilli), and the temperature is slightly cooler than room, about 10-15°C, but this value of ∆G° suggests that near total biological oxidation is possible.

The Detroit plant, like most others, do this biological oxidation treatment using either large stirred tanks, of million gallon volume or so, or in flow reactors with a large fraction of cellular-material returning as recycle. Recycle is needed also in the stirred tank process because of the low solid content. The reaction is approximately first order in oxygen, carbohydrate, and bacteria. Thus a 50% cell recycle more or less doubles the speed of the reaction. Air is typically bubbled through the reactor to provide the oxygen, but in Detroit, pure oxygen is used. About half the organic carbon is oxidized and the remainder is sent to a settling pond. The decant (top) water is sent for “polishing” and dumped in the river, while the goop (the bottom) is currently dried for burning or carted off for landfill. The Holly, MI sewage plant uses a heterogeneous reactors for the oxidation: a trickle bed followed by a rotating disk contractor. These have higher bio-content and thus lower area demands and separation costs, but there is a somewhat higher capital cost.

A major component of bio-solids is nitrogen. Much of this in enters the form of urea, NH2-CO-NH2. In an oxidizing environment, bacteria turns the urea and other nitrogen compounds into nitrate. Consider the reaction the presence of washing soda, Na2CO3. The urea is turned into nitrate, a product suitable for gun powder manufacture. The value of ∆G° is negative, and the reaction is highly favorable.

NH2-CO-NH2 + Na2CO3 + 4 O2 –> 2 Na(NO3) + 2 CO2 + 2 H2O.     ∆G° = -177.5 kcal/mol

The mixture of nitrates and dry bio-solids is highly flammable, and there was recently a fire in the Detroit biosolids dryer. If we wished to make fertilizer, we’d probably want to replace the drier with a further stage of bio-treatment. In Wisconsin, and on a smaller scale in Oakland MI, biosolids are treated by higher temperature (thermophilic) bacteria in the absence of air, that is anaerobically. Anaerobic digestion produces hydrogen and methane, and produces highly useful forms of organic carbon.

2 (-HCOH-) –> CO2 + CH4        ∆G° = -33.7 Kcal/mol

3 (-HCOH-) + H2O –> -CH2COOH + CO2 +  2 1/2 H2        ∆G° = -21.9 kcal/mol

In a well-designed plant, the methane is recovered to provide heat to the plant, and sometimes to generate power. In Wisconsin, enough methane is produced to cook the fertilizer to sterilization. The product is called “Milorganite” as much of it comes from Milwaukee and much of the nitrate is bound to organics.

Egg-shaped, anaerobic biosolid digestors.

Egg-shaped, anaerobic biosolid digestors, Singapore.

The hydrogen could be recovered too, but typically reacts further within the anaerobic digester. Typically it will reduce the iron oxide in the biosolids from the brown, ferric form, Fe2O3, to black FeO.  In a reducing atmosphere,

Fe2O3 + H2 –> 2 FeO + H2O.

Fe2O3 is the reason leaves turn brown in the fall and is the reason that most poop is brown. FeO is the reason that composted soil is typically black. You’ll notice that swamps are filled with black goo, that’s because of a lack of oxygen at the bottom. Sulphate and phosphorous can be bound to ferrous iron and this is good for fertilizer. Generally you want the reduction reactions to go no further.

Weir dam on the river dour. Used to manage floods, increase residence time, and oxygenate the flow.

Weir dam on the river Dour in Scotland. Dams of this type increase residence time, and oxygenate the flow. They’re good for fish, pollution, and flooding.

When allowed to continue, the hydrogen produced by anaerobic digestion begins to reduce sulfate to H2S.

NaSO4 + 4.5 H2 –>  NaOH + 3H2O + H2S.

I’m running for Oakland county, MI water commissioner, and one of my aims is to stop wasting our biosolids. Oakland produces nearly 1000,000 pounds of dry biosolids per day. This is either a blessing or a curse depending on how we use it.

Another issue, Oakland county dumps unpasteurized, smelly black goo into Lake St. Clair every other week, whenever it rains more than one inch. I’d like to stop this by separating the storm and “sanitary” sewage. There is a capital cost, but it can save money because we’d no longer have to pay to treat our rainwater at the Detroit sewage plant. To clean the storm runoff, I’d use mini wetlands and weir dams to increase residence time and provide oxygen. Done right, it would look beautiful and would avoid the flash floods. It should also bring natural fish back to the Clinton River.

Robert Buxbaum, May 24 – Sept. 15, 2016 Thermodynamics plays a big role in my posts. You can show that, when the global ∆G is negative, there is an increase in the entropy of the universe.