Tag Archives: methanol

Upgrading landfill and digester gas for sale, methanol

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We live in a throw-away society, and the majority of it, eventually makes its way to a landfill. Books, food, grass clippings, tree-products, consumer electronics; unless it gets burnt or buried at sea, it goes to a landfill and is left to rot underground. The product of this rot is a gas, landfill gas, and it has a fairly high energy content if it could be tapped. The composition of landfill gas changes, but after the first year or so, the composition settles down to a nearly 50-50 mix of CO2 and methane. There is a fair amount of water vapor too, plus some nitrogen and hydrogen, but the basic process is shown below for wood decomposition, and the products are CO2  and methane.

System for sewage gas upgrading, uses REB membranes.

C6 H12 O6  –> 3 CO2  + 3 CH4 

This mix can not be put in the normal pipeline: there is too much CO2  and there are too many other smelly or condensible compounds (water, methanol, H2S…). This gas is sometimes used for heat on site, but there is a limited need for heat near a landfill. For the most part it is just vented or flared off. The waste of a potential energy source is an embarrassment. Besides, we are beginning to notice that methane causes global-warming with about 50 times the effect of CO2, so there is a strong incentive to capture and burn this gas, even if you have no use for the heat. I’d like to suggest a way to use the gas.

We sell small membrane modules too.

The landfill gas can be upgraded by removing the CO2. This can be done via a membrane, and REB Research sells a membranes that can do this. Other companies have other membranes that can do this too, but ours are smaller, and more suitable to small operations in my opinion. Our membrane are silicone-based. They retain CH4 and CO and hydrogen, while extracting water, CO2 and H2S, see schematic. The remainder is suited for local use in power generation, or in methanol production. It can also be used to run trucks. Also the gas can be upgraded further and added to a pipeline for shipping elsewhere. The useless parts can be separated for burial. Find these membranes on the REB web-site under silicone membranes.

Garbage trucks in New York powered by natural gas. They could use landfill gas.

There is another gas source whose composition is nearly identical to that of landfill gas; it’s digester gas, the output of sewage digesters. I’ve written about sewage treatment mostly in terms of aerobic bio treatment, for example here, but sewage can be treated anaerobically too, and the product is virtually identical to landfill gas. I think it would be great to power garbage trucks and buses with this. Gas. In New York, currently, some garbage trucks are powered by natural gas.

As a bonus, here’s how to make methanol from partially upgraded landfill or digester gas. As a first step 2/3 of the the CO2 removed. The remained will convert to methanol. by the following overall chemistry:

3 CH4 + CO2 + 2 H2O –> 4 CH3OH. 

When you removed the CO2., likely most of the water will leave with it. You add back the water as steam and heat to 800°C over Ni catalyst to make CO and H2. That’s done at about 800°C and 200 psi. Next, at lower temperature, with an appropriate catalyst you recombine the CO and H2 into methanol; with other catalysts you can make gasoline. These are not trivial processes, but they are doable on a smallish scale, and make economic sense where the methane is essentially free and there is no CNG customer. Methanol sells for $1.65/gal when sold by the tanker full, but $5 to $10/gal at the hardware store. That’s far higher than the price of methane, and methanol is far easier to ship and sell in truckload quantities.

Robert Buxbaum, June 8, 2021

Hydrogen versus Battery Power

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There are two major green energy choices that people are considering to power small-to-medium size, mobile applications like cars and next generation, drone airplanes: rechargeable, lithium-ion batteries and hydrogen /fuel cells. Neither choice is an energy source as such, but rather a clean energy carrier. That is, batteries and fuel cells are ways to store and concentrate energy from other sources, like solar or nuclear plants for use on the mobile platform.

Of these two, rechargeable batteries are the more familiar: they are used in computers, cell phones, automobiles, and the ill-fated, Boeing Dreamliner. Fuel cells are less familiar but not totally new: they are used to power most submarines and spy-planes, and find public use in the occasional, ‘educational’ toy. Fuel cells provided electricity for the last 30 years of space missions, and continue to power the international space station when the station is in the dark of night (about half the time). Batteries have low energy density (energy per mass or volume) but charging them is cheap and easy. Home electricity costs about 12¢/kWhr and is available in every home and shop. A cheap transformer and rectifier is all you needed to turn the alternating current electricity into DC to recharge a battery virtually anywhere. If not for the cost and weight of the batteries, the time to charge the battery (usually and hour or two), batteries would be the obvious option.

Two obvious problems with batteries are the low speed of charge and the annoyance of having to change the battery every 500 charges or so. If one runs an EV battery 3/4 of the way down and charges it every week, the battery will last 8 years. Further, battery charging takes 1-2 hours. These numbers are acceptable if you use the car only occasionally, but they get more annoying the more you use the car. By contrast, the tanks used to hold gasoline or hydrogen fill in a matter of minutes and last for decades or many thousands of fill-cycles.

Another problem with batteries is range. The weight-energy density of batteries is about 1/20 that of gasoline and about 1/10 that of hydrogen, and this affects range. While gasoline stores about 2.5 kWhr/kg including the weight of the gas tank, current Li-Ion batteries store far less than this, about 0.15 kWhr/kg. The energy density of hydrogen gas is nearly that of gasoline when the efficiency effect is included. A 100 kg of hydrogen tank at 10,000 psi will hold 8 kg of hydrogen, or enough to travel about 350 miles in a fuel-cell car. This is about as far as a gasoline car goes carrying 60 kg of tank + gasoline. This seems acceptable for long range and short-range travel, while the travel range with eVs is more limited, and will likely remain that way, see below.

The volumetric energy density of compressed hydrogen/ fuel cell systems is higher than for any battery scenario. And hydrogen tanks are far cheaper than batteries. From Battery University. http://batteryuniversity.com/learn/article/will_the_fuel_cell_have_a_second_life

The volumetric energy density of compressed hydrogen/ fuel cell systems is higher than for any battery scenario. And hydrogen tanks are far cheaper than batteries. From Battery University. http://batteryuniversity.com/learn/article/will_the_fuel_cell_have_a_second_life

Cost is perhaps the least understood problem with batteries. While electricity is cheap (cheaper than gasoline) battery power is expensive because of the high cost and limited life of batteries. Lithium-Ion batteries cost about $2000/kWhr, and give an effective 500 charge/discharge cycles; their physical life can be extended by not fully charging them, but it’s the same 500 cycles. The effective cost of the battery is thus $4/kWhr (The battery university site calculates $24/kWhr, but that seems overly pessimistic). Combined with the cost of electricity, and the losses in charging, the net cost of Li-Ion battery power is about $4.18/kWhr, several times the price of gasoline, even including the low efficiency of gasoline engines.

Hydrogen prices are much lower than battery prices, and nearly as low as gasoline, when you add in the effect of the high efficiency fuel cell engine. Hydrogen can be made on-site and compressed to 10,000 psi for less cost than gasoline, and certainly less cost than battery power. If one makes hydrogen by electrolysis of water, the cost is approximately 24¢/kWhr including the cost of the electrolysis unit.While the hydrogen tank is more expensive than a gasoline tank, it is much cheaper than a battery because the technology is simpler. Fuel cells are expensive though, and only about 50% efficient. As a result, the as-used cost of electrolysis hydrogen in a fuel cell car is about 48¢/kWhr. That’s far cheaper than battery power, but still not cheap enough to encourage the sale of FC vehicles with the current technology.

My company, REB Research provides another option for hydrogen generation: The use of a membrane reactor to make it from cheap, easy to transport liquids like methanol. Our technology can be used to make hydrogen either at the station or on-board the car. The cost of hydrogen made this way is far cheaper than from electrolysis because most of the energy comes from the methanol, and this energy is cheaper than electricity.

In our membrane reactors methanol-water (65-75% Methanol), is compressed to 350 psi, heated to 350°C, and reacted to produce hydrogen that is purified as it is made. CH3OH + H2O –> 3H2 + CO2, with the hydrogen extracted through a membrane within the reactor.

The hydrogen can be compressed to 10,000 psi and stored in a tank on board an automobile or airplane, or one can choose to run this process on-board the vehicle and generate it from liquid fuel as-needed. On-board generation provides a saving of weight, cost, and safety since you can carry methanol-water easily in a cheap tank at low pressure. The energy density of methanol-water is about 1/2 that of gasoline, but the fuel cell is about twice as efficient as a gasoline engine making the overall volumetric energy density about the same. Not including the fuel cell, the cost of energy made this way is somewhat lower than the cost of gasoline, about 25¢/kWhr; since methanol is cheaper than gasoline on a per-energy basis. Methanol is made from natural gas, coal, or trees — non-imported, low cost sources. And, best yet, trees are renewable.

What is the best hydrogen storage medium?

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Answering best questions is always tricky since best depends on situation, but I’ll cover some hydrogen storage options here, and I’ll try to explain where our product options (cylinder gas purifiers and methanol-water reformers) fit in.

The most common laboratory option for hydrogen storage is inside a tank; typically this tank is made of steel, but it can be made of aluminum, fiberglass or carbon fiber. Tanks are the most convenient source for small volume users since they are instantly ready for delivery at any pressure up to the storage pressure; typically that’s 2000 psi (135 atm) though 10,000 (1350 atm) is available by special order. The maximum practical density for this storage is about 50 g/liter, but this density ignores the weight of the tank. The tank adds a factor of 20 or to the weight, making tanks a less-favored option for mobile users. Tanks also add significantly to the cost. They also tend to add impurities to the gas, and there’s a safety issue too: tanks sometimes fall over, and compressed gas can explode. For small-volume, non-mobile users, one can address safety by chaining up ones tank and adding a metal membrane hydrogen purifier; This is one of our main products.

Another approach is liquid hydrogen; The density of liquid hydrogen is higher than of gas, about 68 g/liter, and you don’t need as a tank that’s a big or heavy. One problem is that you have to keep the liquid quite cold, about 25 K. There are evaporative losses too, and if the vent should freeze shut you will get a massive explosion. This is the storage method preferred by large users, like NASA.

Moving on to metal hydrides. These are heavy and rather expensive but they are safer than the two previous options. To extract hydrogen from a metal hydride bed the entire hydride bed has to be heated, and this adds complexity. To refill the bed, it generally has to be cooled, and this too adds complexity. Generally, you need a source of moderately high pressure, clean, dry hydrogen to recharge a bed. You can get this from either an electrolysis generator, with a metal membrane hydrogen purifier, or by generating the hydrogen from methanol using one of our membrane reactor hydrogen generators.

Borohydrides are similar to metal hydrides, but they can flow. Sorry to say, they are more expensive than normal metal hydrides and they can not be regenerated.They are ideal for some military use

And now finally, chemical materials: water, methanol, and ammonia. Chemical compounds are a lot cheaper than metal hydrides or metal borohydrides, and tend to be far more readily available and transportable being much lighter in weight. Water and/or methanol contains 110 gm of H2/liter;  ammonia contains 120 gms/liter, and the tanks are far lighter and cheaper too. Polyethylene jugs weighing a few ounces suffices to transport gallon quantities of water or methanol and, while not quite as light, relatively cheap metallic containers suffice to hold and transport ammonia.

The optimum choice of chemical storage varies with application and customer need. Water is the safest option, but it can freeze in the cold, and it does not contain its own chemical energy. The energy to split the water has to come externally, typically from electricity via electrolysis. This makes water impractical for mobile applications. Also, the hydrogen generated from water electrolysis tends to be impure, a problem for hydrogen that is intended for storage or chemical manufacture. Still, there is a big advantage to forming hydrogen from something that is completely non-toxic, non-flammable, and readily available, and water definitely has a place among the production options.

Methanol contains its own chemical energy, so hydrogen can be generated by heating alone (with a catalyst), but it is toxic to drink and it is flammable. I’ve found a  my unique way of making hydrogen from methanol-water using  a membrane reactor. Go to my site for sales and other essays.

Finally, ammonia provides it’s own chemical energy like methanol, and is flammable, like methanol; we can convert it to hydrogen with our membrane reactors like we can methanol, but ammonia is far more toxic than methanol, possessing the power to kill with both its vapors and in liquid form. We’ve made ammonia reformers, but prefer methanol.

How and why membrane reactors work

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Here is a link to a 3 year old essay of mine about how membrane reactors work and how you can use them to get past the normal limits of thermodynamics. The words are good, as is the example application, but I think I can write a shorter version now. Also, sorry to say, when I wrote the essay I was just beginning to make membrane reactors; my designs have gotten simpler since.

At left, for example, is a more modern, high pressure membrane reactor design. A common size is  72 tube reactor assembly; high pressure. The area around the shell is used for heat transfer. Normally the reactor would sit with this end up, and the tube area filled or half-filled with catalyst, e.g. for the water gas shift reaction, CO + H2O –> CO2 + H2 or for the methanol reforming CH3OH + H2O –> 3H2 + CO2, or ammonia cracking 2NH3 –> N2 + 3H2. According to normal thermodynamics, the extent of reaction for these reactions will be negatively affected by pressure (WGS is unaffected). Separation of the hydrogen generally requires high pressure and a separate step or two. This setup combines the steps of reaction with separation, give you ultra high purity, and avoids the normal limitations of thermodynamics.

Once equilibrium is reached in a normal reactor, your only option to drive the reaction isby adjusting the temperature. For the WGS, you have to operate at low temperatures, 250- 300 °C, if you want high conversion, and you have to cool externally to remove the heat of reaction. In a membrane reactor, you can operate in your preferred temperature ranges and you don’t have to work so hard to remove, or add heat. Typically with a MR, you want to operate at high reactor pressures, and you want to extract hydrogen at a lower pressure. The pressure difference between the reacting gas and the extracted hydrogen allows you to achieve high reaction extents (high conversions) at any temperature. The extent is higher because you are continuously removing product – H2 in this case.

Here’s where we sell membrane reactors; we also sell catalyst and tubes.

Hydrogen addition to an automobile engine

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Today, I began a series of experiments putting hydrogen into my car engine. Hydrogen is a combustion promotor, increasing the flame speed significantly, even at low compositions, and it has a very high octane value, so it does not cause pre-ignition. I used my Chevy Malibu, shown, and generated the hydrogen using one of our (REB Research’s) methanol-reformer hydrogen generators. I used a small hydrogen generator we sell for gas chromatographic use, and put 280 ccm hydrogen into engine, as shown. This is enough to provide 1% of the energy content about during idle.

I’ve not measured mpg change yet (as a stationary experiment the mpg is 0), but was really looking for outward signs of knock or other engine problems. Adding 280 ccm of hydrogen should increase the flame speed by ~2%, which should increase the degree of high pressure combustion, and this should increase the mpg by about 3% or 4% if you don’t include the hydrogen energy. So far, I saw no ill effects: no ill sounds and no check engine lights.

H2_boost_in_Buxbaum_Malibu

Hydrogen added to a Chevy Malibu engine at REB Research

About half the hydrogen energy comes from waste heat of the engine, and half the methanol. Either way this energy is very cheap: methanol costs about $1.20/gal, about half of what gasoline does on a per-energy basis.  Next step is to make my hydrogen generator mobile, and check the effect on mpg. I’m glad it worked OK so far. There was a reporter watching.

New hydrogen generator for gas chromatographic use

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Shown below is our latest product: a lower cost hydrogen generator, designed for use to provide the carrier and flame gas for gas chromatography. It’s our highest pressure, lowest hydrogen output product, outputting hydrogen at up to 90 psi. The output is still higher than any other generator in the GC space, and the purity is greater; 99.99995%, good enough to be used as the carrier gas, not just the detector gas. Fairly low price too.http://www.rebresearch.com/
Photo: Our latest new product: a lower cost, hydrogen generator for use with gas chromatography. It's our highest pressure, lowest hydrogen output product, but the output is still higher than any other in the GC space, and the price is less at that purity. </p><br /> <p>http://www.rebresearch.com/
As always, the hydrogen is made from methanol-water reforming in a membrane reactor, but we did a couple of things differently from previous designs. We closed up the front more so you don’t stick your fingers where they don’t belong. We also have a more-transpartent tank so you have a better idea what the liquid level is. The use of the membrane reactor is why our hydrogen is purer; we go through a metal membrane and our competition, (Porter, etc) uses only a desiccant.