Category Archives: REB Research products

Chemical engineers and boilers, ‘I do anything’

1 Reply

One of the problems I run into trying to hire chemical engineers is that their background is so varied that they imagine they can do anything. Combine this with a willingness to try to do anything, and the job interview can go like this.

Me: You have a great resume. I suppose you know that our company is a leader in hydrogen engineering (in my case). Tell me, what do you see yourself doing at our company?

Engineer: I don’t know. I do anything and everything.

Me: That covers a lot of ground. Is there something that you do particularly well, or that you would particularly like to do here?

Engineer.: Anything, really.

Me: Do you see yourself making coffee?

Engineer: I could do that, but was thinking of something with more … responsibility.

Me: OK. Could you design and build a 5 kW, gas-fired boiler?

Engineer: Himm. How much coffee did you say you guys drink?

Current version of our H2 generators (simplified) and the combustion-heated modification I'm working on.

Current version of our H2 generators (simplified) and the combustion-heated modification I’m working on.

Not quite where I was going with that. The relevance of this joke is that I’m finally getting around to redesigning our hydrogen generators so that they are heated by waste-gas combustion instead of electricity. That was the plan originally, and it appears in almost all of my patents. But electricity is so easy to deal with and control that all REB generators have been heated this way, even the largest.

The current and revised processes are shown in the figure at right. Our general process is to make ultra pure hydrogen from methanol and water in one step by the following reaction:

CH3OH + H2O –> CO2  + 3 H2.

done in a membrane reactor (see advantages). My current thought is to make the first combustion heated hydrogen generator have an output about 2/3 as large as our largest. That is, to produce 100 scfh, or 50 slpm, or 6 kg of H2/ day. This could be advantageous for people trying to fuel fork lifts or a hybrid, fuel cell car; a car could easily carry 12 kg of hydrogen, allowing it to go an extra 300 miles.

The generator with this output will need a methanol-water feed rate of about 2/3 gal per hour (about 80¢/worth pre hour), and will need a heat rate of 2.5 to 3 kW. A key design issue is that I have to be sure not to extract too much energy value from the feed because, if there’s not enough energy in the waste gas, the fire could go out. That is, nearly pure CO2 doesn’t burn. Alternately, if there is too much flow to the flame or too much energy content, there might be over-heating. In order to avoid the flame going out, I have a pilot flame that turns off the flow if it goes out. I also plan to provide 30% or so of the reactor heat about 800 W, by burning non-wast gas, natural gas in this iteration. My plan is to use this flow to provide most of the temperature control, but to provide secondary control by (and safety) by venting some of the off-gas if the reactor gets hotter than a set limit. Early experiments suggest it should work.

The business side of this is still unknown. Perhaps this would provide military power or cabins in the woods. Perhaps ship-board auxiliary power or balloons, or hydrogen fueling stations, or perhaps it will be used for chemical applications. With luck, it’ll sell to someone who needs hydrogen.

Robert E. Buxbaum. December 4, 2015. By the way, hydrogen isn’t as flammable as you might think.

Air swimmer at REB Research

Leave a reply

Birds got to swim and fish got to fly. Gonna love that hydrogen till the day I die. Here’s a movie of our hydrogen-filled air swimmer, a fish-blimp at REB Research. My hope is that this thing will help us sell hydrogen generators — perhaps to folks who fly military balloons, or those who fly hydrogen balloons for sport. On the other hand, the swimmer is a lot of fun to play with — and I got to show it off to a first grade class!

Aside from balloon fliers, military and otherwise, the sort of customers I’d hoped to attract were those building fueling stations for fuel cell cars or drone airplanes, and those running multiple gas chromatographs or adding hydrogen to car or diesel engine. Even small amounts of hydrogen added to a standard engine will reduce pollution significantly, add raise mileage too: a plus for a company like VW.

Dr. Robert E. Buxbaum, December 2, 2015. I should mention that hydrogen balloons are no where near as unsafe as people think. Here’s a movie I made of lighting a hydrogen filled balloon with a cigar.

my electric cart of the future

3 Replies
Buxbaum and Sperka cart of future

Buxbaum and Sperka show off the (shopping) cart of future, Oak Park parade July 4, 2015.

A Roman chariot did quite well with only 1 horse-power, while the average US car requires 100 horses. Part of the problem is that our cars weigh more than a chariot and go faster, 80 mph vs of 25 mph. But most city applications don’t need all that weight nor all of that speed. 20-25 mph is fine for round-town errands, and should be particularly suited to use by young drivers and seniors.

To show what can be done with a light vehicle that only has to go 20 mph, I made this modified shopping cart, and fitted it with a small, 1 hp motor. I call it the cart-of the future and paraded around with it at our last 4th of July parade. It’s high off the ground for safety, reasonably wide for stability, and has the shopping cart cage and seat-belts for safety. There is also speed control. We went pretty slow in the parade, but here’s a link to a video of the cart zipping down the street at 17.5 mph.

In the 2 months since this picture was taken, I’ve modified the cart to have a chain drive and a rear-wheel differential — helpful for turning. My next modification, if I get to it, will be to switch to hydrogen power via a fuel cell. One of the main products we make is hydrogen generators, and I’m hoping to use the cart to advertise the advantages of hydrogen power.

Robert E. Buxbaum, August 28, 2015. I’m the one in the beige suit.

My latest invention: improved fuel cell reformer

1 Reply

Last week, I submitted a provisional patent application for an improved fuel reformer system to allow a fuel cell to operate on ordinary, liquid fuels, e.g. alcohol, gasoline, and JP-8 (diesel). I’m attaching the complete text of the description, below, but since it is not particularly user-friendly, I’d like to add a small, explanatory preface. What I’m proposing is shown in the diagram, following. I send a hydrogen-rich stream plus ordinary fuel and steam to the fuel cell, perhaps with a pre-reformer. My expectation that the fuel cell will not completely convert this material to CO2 and water vapor, even with the pre-reformer. Following the fuel cell, I then use a water-gas shift reactor to convert product CO and H2O to H2 and CO2 to increase the hydrogen content of the stream. I then use a semi-permeable membrane to extract the waste CO2 and water. I recirculate the hydrogen and the rest of the water back to the fuel cell to generate extra power, prevent coking, and promote steam reforming. I calculate the design should be able to operate at, perhaps 0.9 Volt per cell, and should nearly double the energy per gallon of fuel compared to ordinary diesel. Though use of pure hydrogen fuel would give better mileage, this design seems better for some applications. Please find the text following.

Use of a Water-Gas shift reactor and a CO2 extraction membrane to improve fuel utilization in a solid oxide fuel cell system.

Inventor: Dr. Robert E. Buxbaum, REB Research, 12851 Capital St, Oak Park, MI 48237; Patent Pending.

Solid oxide fuel cells (SOFCs) have improved over the last 10 years to the point that they are attractive options for electric power generation in automobiles, airplanes, and auxiliary power supplies. These cells operate at high temperatures and tolerate high concentrations of CO, hydrocarbons and limited concentrations of sulfur (H2S). SOFCs can operate on reformate gas and can perform limited degrees of hydrocarbon reforming too – something that is advantageous from the stand-point of fuel logistics: it’s far easier to transport a small volume of liquid fuel that it is a large volume of H2 gas. The main problem with in-situ reforming is the danger of coking the fuel cell, a problem that gets worse when reforming is attempted with the more–desirable, heavier fuels like gasoline and JP-8. To avoid coking the fuel cell, heavier fuels are typically reforming before hand in a separate reactor, typically by partial oxidation at auto-thermal conditions, a process that typically adds nitrogen and results in the inability to use the natural heat given off by the fuel cell. Steam reforming has been suggested as an option (Chick, 2011) but there is not enough heat released by the fuel cell alone to do it with the normal fuel cycles.

Another source of inefficiency in reformate-powered SOFC systems is basic to the use of carbon-containing fuels: the carbon tends to leave the fuel cell as CO instead of CO2. CO in the exhaust is undesirable from two perspectives: CO is toxic, and quite a bit of energy is wasted when the carbon leaves in this form. Normally, carbon can not leave as CO2 though, since CO is the more stable form at the high temperatures typical of SOFC operation. This patent provides solutions to all these problems through the use of a water-gas shift reactor and a CO2-extraction membrane. Find a drawing of a version of the process following.

RE. Buxbaum invention: A suggested fuel cycle to allow improved fuel reforming with a solid oxide fuel cell

RE. Buxbaum invention: A suggested fuel cycle to allow improved fuel reforming with a solid oxide fuel cell

As depicted in Figure 1, above, the fuel enters, is mixed with steam or partially boiled water, and heated in the rectifying heat exchanger. The hot steam + fuel mix then enters a steam reformer and perhaps a sulfur removal stage. This would be typical steam reforming except for a key difference: the heat for reforming comes (at least in part) from waste heat of the SOFC. Normally speaking there would not be enough heat, but in this system we add a recycle stream of H2-rich gas to the fuel cell. This stream, produced from waste CO in a water-gas shift reactor (the WGS) shown in Figure 1. This additional H2 adds to the heat generated by the SOFC and also adds to the amount of water in the SOFC. The net effect should be to reduce coking in the fuel cell while increasing the output voltage and providing enough heat for steam reforming. At least, that is the thought.

SOFCs differ from proton conducting FCS, e.g. PEM FCs, in that the ion that moves is oxygen, not hydrogen. As a result, water produced in the fuel cell ends up in the hydrogen-rich stream and not in the oxygen stream. Having this additional water in the fuel stream of the SOFC can promote fuel reforming within the FC. This presents a difficulty in exhausting the waste water vapor in that a means must be found to separate it from un-combusted fuel. This is unlike the case with PEM FCs, where the waste water leaves with the exhaust air. Our main solution to exhausting the water is the use of a membrane and perhaps a knockout drum to extract it from un-combusted fuel gases.

Our solution to the problem of carbon leaving the SOFC as CO is to react this CO with waste H2O to convert it to CO2 and additional H2. This is done in a water gas shift reactor, the WGS above. We then extract the CO2 and remaining, unused water through a CO2- specific membrane and we recycle the H2 and unconverted CO back to the SOFC using a low temperature recycle blower. The design above was modified from one in a paper by PNNL; that paper had neither a WGS reactor nor a membrane. As a result it got much worse fuel conversion, and required a high temperature recycle blower.

Heat must be removed from the SOFC output to cool it to a temperature suitable for the WGS reactor. In the design shown, the heat is used to heat the fuel before feeding it to the SOFC – this is done in the Rectifying HX. More heat must be removed before the gas can go to the CO2 extractor membrane; this heat is used to boil water for the steam reforming reaction. Additional heat inputs and exhausts will be needed for startup and load tracking. A solution to temporary heat imbalances is to adjust the voltage at the SOFC. The lower the voltage the more heat will be available to radiate to the steam reformer. At steady state operation, a heat balance suggests we will be able to provide sufficient heat to the steam reformer if we produce electricity at between 0.9 and 1.0 Volts per cell. The WGS reactor allows us to convert virtually all the fuel to water and CO2, with hardly any CO output. This was not possible for any design in the PNNL study cited above.

The drawing above shows water recycle. This is not a necessary part of the cycle. What is necessary is some degree of cooling of the WGS output. Boiling recycle water is shown because it can be a logistic benefit in certain situations, e.g. where you can not remove the necessary CO2 without removing too much of the water in the membrane module, and in mobile military situations, where it’s a benefit to reduce the amount of material that must be carried. If water or fuel must be boiled, it is worthwhile to do so by cooling the output from the WGS reactor. Using this heat saves energy and helps protect the high-selectivity membranes. Cooling also extends the life of the recycle blower and allows the lower-temperature recycle blowers. Ideally the temperature is not lowered so much that water begins to condense. Condensed water tends to disturb gas flow through a membrane module. The gas temperatures necessary to keep water from condensing in the module is about 180°C given typical, expected operating pressures of about 10 atm. The alternative is the use of a water knockout and a pressure reducer to prevent water condensation in membranes operated at lower temperatures, about 50°C.

Extracting the water in a knockout drum separate from the CO2 extraction has the secondary advantage of making it easier to adjust the water content in the fuel-gas stream. The temperature of condensation can then be used to control the water content; alternately, a separate membrane can extract water ahead of the CO2, with water content controlled by adjusting the pressure of the liquid water in the exit stream.

Some description of the membrane is worthwhile at this point since a key aspect of this patent – perhaps the key aspect — is the use of a CO2-extraction membrane. It is this addition to the fuel cycle that allows us to use the WGS reactor effectively to reduce coking and increase efficiency. The first reasonably effective CO2 extraction membranes appeared only about 5 years ago. These are made of silicone polymers like dimethylsiloxane, e.g. the Polaris membrane from MTR Inc. We can hope that better membranes will be developed in the following years, but the Polaris membrane is a reasonably acceptable option and available today, its only major shortcoming being its low operating temperature, about 50°C. Current Polaris membranes show H2-CO2 selectivity about 30 and a CO2 permeance about 1000 Barrers; these permeances suggest that high operating pressures would be desirable, and the preferred operation pressure could be 300 psi (20 atm) or higher. To operate the membrane with a humid gas stream at high pressure and 50°C will require the removal of most of the water upstream of the membrane module. For this, I’ve included a water knockout, or steam trap, shown in Figure 1. I also include a pressure reduction valve before the membrane (shown as an X in Figure 1). The pressure reduction helps prevent water condensation in the membrane modules. Better membranes may be able to operate at higher temperatures where this type of water knockout is not needed.

It seems likely that, no matter what improvements in membrane technology, the membrane will have to operate at pressures above about 6 atm, and likely above about 10 atm (upstream pressure) exhausting CO2 and water vapor to atmosphere. These high pressures are needed because the CO2 partial pressure in the fuel gas leaving the membrane module will have to be significantly higher than the CO2 exhaust pressure. Assuming a CO2 exhaust pressure of 0.7 atm or above and a desired 15% CO2 mol fraction in the fuel gas recycle, we can expect to need a minimum operating pressure of 4.7 atm at the membrane. Higher pressures, like 10 or 20 atm could be even more attractive.

In order to reform a carbon-based fuel, I expect the fuel cell to have to operate at 800°C or higher (Chick, 2011). Most fuels require high temperatures like this for reforming –methanol being a notable exception requiring only modest temperatures. If methanol is the fuel we will still want a rectifying heat exchanger, but it will be possible to put it after the Water-Gas Shift reactor, and it may be desirable for the reformer of this fuel to follow the fuel cell. When reforming sulfur-containing fuels, it is likely that a sulfur removal reactor will be needed. Several designs are available for this; I provide references to two below.

The overall system design I suggest should produce significantly more power per gm of carbon-based feed than the PNNL system (Chick, 2011). The combination of a rectifying heat exchange, a water gas reactor and CO2 extraction membrane recovers chemical energy that would otherwise be lost with the CO and H2 bleed steam. Further, the cooling stage allows the use of a lower temperature recycle pump with a fairly low compression ratio, likely 2 or less. The net result is to lower the pump cost and power drain. The fuel stream, shown in orange, is reheated without the use of a combustion pre-heater, another big advantage. While PNNL (Chick, 2011) has suggested an alternative route to recover most of the chemical energy through the use of a turbine power generator following the fuel cell, this design should have several advantages including greater reliability, and less noise.

Claims:

1.   A power-producing, fuel cell system including a solid oxide fuel cell (SOFC) where a fuel-containing output stream from the fuel cell goes to a regenerative heat exchanger followed by a water gas shift reactor followed by a membrane means to extract waste gases including carbon dioxide (CO2) formed in said reactor. Said reactor operating a temperatures between 200 and 450°C and the extracted carbon dioxide leaving at near ambient pressure; the non-extracted gases being recycled to the fuel cell.

Main References:

The most relevant reference here is “Solid Oxide Fuel Cell and Power System Development at PNNL” by Larry Chick, Pacific Northwest National Laboratory March 29, 2011: http://www.energy.gov/sites/prod/files/2014/03/f10/apu2011_9_chick.pdf. Also see US patent  8394544. it’s from the same authors and somewhat similar, though not as good and only for methane, a high-hydrogen fuel.

Robert E. Buxbaum, REB Research, May 11, 2015.

How do technology companies sell stuff?

1 Reply

As the owner of a technology company, REB Research, hydrogen generators and hydrogen purifiers, I spend a fair amount of time trying to sell my stuff, and wondering how other companies connect to potential customers and sell to them. Sales is perhaps the most important area of business success, the one that makes or breaks most businesses — but it was sadly ignored in my extensive college education. Business books are hardly better: they ignore the salesmen (and women); you’re left to imagine sales and profit came of themselves by the insight of the great leader. The great, successful internet companies are applauded for giving away services, and the failed interned companies are barely mentioned. And hardly any book mentions smaller manufacturing businesses, like mine.

So here are some sales thoughts: things I tried, things that worked, and didn’t. I started my company, REB Research, about 20 years ago as a professor at Michigan State University. I figured I knew more about hydrogen purifiers than most of my colleagues, and imagined this knowledge would bring me money (big mistake: I needed customers and profitable sales). My strategy was to publish papers on hydrogen and get some patents as a way to build credibility (worked reasonably well: I write well, do research well, and I’m reasonably inventive). Patents might have been a better strategy if I had not then allowed my patents to be re-written by lawyers. I built the company. while still a professor (a good idea, I think).

When I realized I needed sales, I decided to use trade fairs, conferences, and ads as the big companies did. Most of my budget went for ads in The Thomas Register of American Manufacturing, a fantastically large compendium of who did or sold what (it worked OK, but was since rendered obsolete by the internet). I bought $1500 worth of ads, and got 2 small lines plus a 1/8 page. That’s where I got my sales until the internet cam along. In retrospect, I suspect I should have bought more ads.

William Hamilton cartoon from the new-yorker. I sure wish I could make deals.

William Hamilton cartoon from the new-yorker.

My other big expense was trade fairs. Many big companies sold at trade fairs, events that are widely attended in my field. Sorry to say, I never found customers at these fairs, even when the fairs were dedicated to hydrogen, everyone who’d come by was was selling, and no one was buying, as best I could tell.Somehow, my bigger competitors (also at the fairs) seemed to get interest but I’m not sure if they got sales there. They seem to find sales somewhere, though. Is it me? Am I at the wrong fairs, or are fairs just a scam where no one wins but the organizers? I don’t know. Last month, I spent $2000 for a booth in Ann Arbor, MI, including $350 for inclusion into the promoter’s book and $400 for hand-out literature. As with previous events, few people came by and none showed anything like interest, I got no e-mail addresses and no sales. Some hungry students wandered the stalls for food and freebees, but there was not one person with money in his/her pocket and a relevant project to spend it on. I doubt anyone read the literature they took.

To date, virtually all of my sales have come from the internet. I got on the internet early, and that has helped my placement in Google. I’ve never bought a google ad, but this may change. Instead I was lucky. About 20 years ago, 1994?, I attended a conference at Tufts on membrane reactors, and stayed at a bed-and-breakfast. After the conference let out, the owner of the BnB suggested I visit something that was new at Harvard; a cyber cafe, the second one in the US. They had Macintosh computers and internet explorer a year before the company went public. I was hooked, went home, learned html, and wrote a web-site. I bought my domain name shortly thereafter.

The problem, I don’t know the next big thing. Twitter? Facebook? LinkedIn? I’m on 2 of these 3, and have gotten so sales from social media. I started a blog (you’re reading it), but I still wonder, why are the bigger companies selling more? The main difference I see is they attend a lot more product fairs than I do, have slicker web-sties (not very good ones, I think), and they do print advertising. Perhaps they match their fairs to their products better, or have a broader range of products. People need to see my products somewhere, but where? My latest idea: this week I bought HydrogenPurifier.com. Send me advice, or wish me luck.

Robert E. Buxbaum, flailing entrepreneur, September 10, 2014. Here’s a feedback form, the first time I’m adding one. 

Getting rid of hydrogen

4 Replies

Though most of my company’s business is making hydrogen or purifying it, or consulting about it, we also provide sorbers and membranes that allow a customer to get rid of unwanted hydrogen, or remove it from a space where it is not wanted. A common example is a customer who has a battery system for long-term operation under the sea, or in space. The battery or the metal containment is then found to degas hydrogen, perhaps from a corrosion reaction. The hydrogen may interfere with his electronics, or the customer fears it will reach explosive levels. In one case the customer’s system was monitoring deep oil wells and hydrogen from the well was messing up its fiber optic communications.

img505

Pd-coated niobium screws used to getter hydrogen from electronic packages.

For many of these problems, the simplest solution is an organic hydrogen getter of palladium-catalyst and a labile unsaturated hydrocarbon, e.g. buckminsterfullerene. These hydrogen getters are effective in air or inert gas at temperatures between about -20°C and 150°C. When used in an inert gas the organic is hydrogenated, there is a finite amount of removal per gram of sober. When used in air the catalyst promotes the water-forming reaction, and thus there is a lot more hydrogen removal. Depending on the organic, we can provide gettering to lower temperatures or higher. We’ve a recent patent on an organo-palladium gel to operate to 300°C, suitable for down-well hydrogen removal.

At high temperatures, generally above 100*C, we generally suggest an inorganic hydrogen remover, e.g. our platinum ceria catalyst. This material is suitable for hydrogen removal from air, including from polluted air like that in radioactive waste storage areas. Platinum catalyst works long-term at temperatures between about 0°C and 600°C. The catalyst-sorber also works without air, reducing Ce2O3 to CeO and converting hydrogen irreversibly to water (H2O). As with the organo-Pd getters, there is a finite amount of hydrogen removal per gram when these materials are used in a sealed environment.

Low temperature, Pd-grey coated, Pd-Ag membranes made for the space shuttle to remove hydrogen from the drinking water at room temperature. The water came from the fuel cells.

Low temperature, metal membranes made for NASA to remove H2 from  drinking water at room temperature.

Another high temperature hydrogen removal option is metallic getters, e.g. yttrium or vanadium-titanium alloy. These metals require temperatures in excess of 100°C to be effective, and typically do not work well in air. They are best suited for removing hydrogen a vacuum or inert gas, converting it to metallic hydride. The thermodynamics of hydriding is such that, depending on the material, these getters can extract hydrogen even at temperatures up to 700°C, and at very low hydrogen pressures, below 10-9 torr. For operation in air or at 100-400°C we typically provide these getters coated with palladium to increase the hydrogen sorption rate. A fairly popular product is palladium-coated niobium screws 4-40 x 1/4″. Each screw will remove over 2000 sec of hydrogen at temperatures up to 400°C. We also provide oxygen, nitrogen and water getters. They work on the same principle, but form metallic oxides or nitrides instead of hydrides.

Our last, and highest-end, hydrogen-removal option is to provide metallic membranes. These don’t remove the hydrogen as such, but transfer it elsewhere. We’ve provided these for the space shuttle, and to the nuclear industry so that hydrogen can be vented from nuclear reactors before it has a chance to build up and case damage or interfere with heat transfer. Because nothing is used up, these membranes work, essentially forever. The Fukushima reactor explosions were from corrosion-produced hydrogen that had no acceptable way to vent.

Please contact us for more information, e.g. by phone at 248-545-0155, or check out the various sorbers in our web-site. Robert Buxbaum, May 5, 2014.

Hydrogen cars and buses are better than Tesla

17 Replies

Hydrogen fueled cars and buses are as clean to drive as battery vehicles and have better range and faster fueling times. Cost-wise, a hydrogen fuel tank is far cheaper and lighter than an equivalent battery and lasts far longer. Hydrogen is likely safer because the tanks do not carry their oxidant in them. And the price of hydrogen is relatively low, about that of gasoline on a per-mile basis: far lower than batteries when the cost of battery wear-out is included. Both Presidents Clinton and Bush preferred hydrogen over batteries, but the current administration favors batteries. Perhaps history will show them correct, but I think otherwise. Currently, there is not a hydrogen bus, car, or boat making runs at Disney’s Experimental Community of Tomorrow (EPCOT), nor is there an electric bus car or boat. I suspect it’s a mistake, at least convening the lack of a hydrogen vehicle. 

The best hydrogen vehicles on the road have more range than the best electric vehicle, and fuel faster. The hydrogen powered, Honda Clarity debuted in 2008. It has a 270 mile range and takes 3-5 minutes to fuel with hydrogen at 350 atm, 5150 psi. By contrast, the Tesla S-sedan that debuted in 2012 claims only a 208 mile range for its standard, 60kWh configuration (the EPA claims: 190 miles) and requires three hours to charge using their fastest charger, 20 kW.

What limits the range of battery vehicles is that the stacks are very heavy and expensive. Despite using modern lithium-ion technology, Tesla’s 60 kWh battery weighs 1050 lbs including internal cooling, and adds another 250 lbs to the car for extra structural support. The Clarity fuel system weighs a lot less. The hydrogen cylinders weigh 150 lb and require a fuel cell stack (30 lb) and a smaller lithium-ion battery for start-up (90 lb). The net effect is that the Clarity weighs 3582 lbs vs 4647 lbs for the Tesla S. This extra weight of the Tesla seems to hurt its mileage by about 10%. The Tesla gets about 3.3 mi/kWh or 0.19 mile/lb of battery versus 60 miles/kg of hydrogen for the Clarity suggesting  3.6 mi/kWh at typical efficiencies. 

High pressure hydrogen tanks are smaller than batteries and cheaper per unit range. The higher the pressure the smaller the tank. The current Clarity fuels with 350 atm, 5,150 psi hydrogen, and the next generation (shown below) will use higher pressure to save space. But even with 335 atm hydrogen (5000 psi) a Clarity could fuel a 270 mile range with four, 8″ diameter tanks (ID), 4′ long. I don’t know how Honda makes its hydrogen tanks, but suitable tanks might be made from 0.065″ Maranging (aged) stainless steel (UTS = 350,000 psi, density 8 g/cc), surrounded by 0.1″ of aramid fiber (UTS = 250,000 psi, density = 1.6 g/cc). With this construction, each tank would weigh 14.0 kg (30.5 lbs) empty, and hold 11,400 standard liters, 1.14 kg (2.5 lb) of hydrogen at pressure. These tanks could cost $1500 total; the 270 mile range is 40% more Than the Tesla S at about 1/10 the cost of current Tesla S batteries The current price of a replacement Tesla battery pack is $12,000, subsidized by DoE; without the subsidy, the likely price would be $40,000.

Next generation Honda fuel cell vehicle prototype at the 2014 Detroit Auto Show.

Next generation Honda fuel cell vehicle prototype at the 2014 Detroit Auto Show.

Currently hydrogen is more expensive than electricity per energy value, but my company has technology to make it cheaply and more cleanly than electricity. My company, REB Research makes hydrogen generators that produce ultra pure hydrogen by steam reforming wow alcohol in a membrane reactor. A standard generator, suitable to a small fueling station outputs 9.5 kg of hydrogen per day, consuming 69 gal of methanol-water. At 80¢/gal for methanol-water, and 12¢/kWh for electricity, the output hydrogen costs $2.50/kg. A car owner who drove 120,000 miles would spend $5,000 on hydrogen fuel. For that distance, a Tesla owner would spend only $4400 on electricity, but would have to spend another $12,000 to replace the battery. Tesla batteries have a 120,000 mile life, and the range decreases with age. 

For a bus or truck at EPCOT, the advantages of hydrogen grow fast. A typical bus is expected to travel much further than 120,000 miles, and is expected to operate for 18 hour shifts in stop-go operation getting perhaps 1/4 the miles/kWh of a sedan. The charge time and range advantages of hydrogen build up fast. it’s common to build a hydrogen bus with five 20 foot x 8″ tanks. Fueled at 5000 psi., such buses will have a range of 420 miles between fill-ups, and a total tank weight and cost of about 600 lbs and $4000 respectively. By comparison, the range for an electric bus is unlikely to exceed 300 miles, and even this will require a 6000 lb., 360 kWh lithium-ion battery that takes 4.5 hours to charge assuming an 80 kW charger (200 Amps at 400 V for example). That’s excessive compared to 10-20 minutes for fueling with hydrogen.

While my hydrogen generators are not cheap: for the one above, about $500,000 including the cost of a compressor, the cost of an 80 kW DC is similar if you include the cost to run a 200 Amp, 400 V power line. Tesla has shown there are a lot of people who value clean, futuristic transport if that comes with comfort and style. A hydrogen car can meet that handily, and can provide the extra comforts of longer range and faster refueling.

Robert E. Buxbaum, February 12, 2014 (Lincoln’s birthday). Here’s an essay on Lincoln’s Gettysburg address, on the safety of batteries, and on battery cost vs hydrogen. My company, REB Research makes hydrogen generators and purifiers; we also consult.

My failed process for wood to green gasoline

2 Replies

Most researchers publish the results of their successful projects, and ignore the rest. It’s an understandable failing given the cost and work to publish and the general sense that the project that flops indicated a loser – researcher. Still, it’s a shame, and I’d like to break from it here to describe a worthwhile project of mine that failed — turning wood into green gasoline. You may come to believe the project worthwhile too, and figure that you might learn from my story some pathways to avoid if you decide to try it. Besides I figure that it’s an interesting tale. All success stories are similar, I find; failure can come in many ways.

Failure can come from incorrect thinking – assumptions that are wrong. One basis of my thinking was the observation that gasoline, for the most part, was crude-oil that had been fluffed up with hydrogen. The density you buy weighs about 5.5 lb/gallon while crude oil weighs 9 lb/gallon. The difference is hydrogen. Perhaps wood too could be turned into gasoline if hydrogen were added. Another insight was that the structure of wood was the structure of a long chain -alcohol,  —(CHOH)-(CHOH)-(CHOH)—. My company had long experience breaking alcohols to make hydrogen. I figured we could do something similar with wood, fluffing up the wood by breaking the long-chain alcohols to short ones.

A possible first reaction step would be to break a C-O-C bond, a ketone bond, with hydrogen:

—(CHOH)-(CH2O)-(CHOH)— + H2 –>  —(CHOH)-CH2OH + CH2OH—

The next reaction step, I imagined was de-oxygenation:

—(CHOH)-CH2OH  +  H2 –>  —(CHOH)-CH3  + H2O

At this point, we are well on the way to making gasoline, or making a gasoline-relevant alcohol like C6H11-OH. The reactions I wanted were exothermic, meaning they would probably “go” — in actuality -∆G is the determinate of reaction favorability, but usually a -∆H and -∆G go together. Of course there are other reactions that I could have worried about –Ones that produce nasty goop. Among these:

–(CHOH)-(CH2O)-(CHOH)—  –> –(CO)-(C)-(CHOH)— + H2O +H2

I didn’t worry about these reactions because I figured I could outrun them using the right combination of a high hydrogen pressure, the right (low) temperature and the right catalyst. I may have been wrong. Then again, perhaps I picked the wrong catalyst – Fe2O3/ rust, or the wrong set of conditions. I picked Fe2O3 because it was cheap and active.

I convinced myself that Fe2O3 was sufficiently specific to get the product to a good 5-6 carbon compounds for gasoline. Wood celluloses are composed of five and six-carbon ring structure, and the cost of wood is very low per energy. What could go wrong? I figured that starting with these 5-6 carbon ring structures, virtually guaranteed getting high octane products. With the low cost and all the heat energy of the wood, wood + H2 seemed like a winning way to store and transport energy. If i got 6 carbon alcohols and similar compounds they’d have high-octane and the right vapor pressures and the products should be soluble in ordinary gasoline.

And the price was right; gasoline was about $3.50/ gallon, while wood was essentially free.  Hydrogen isn’t that expensive, even using electrolysis, and membrane reactors (a major product of our company) had the potential to make it cheaper. Wood + Hydrogen seemed like the cheaper version of syngas: CO +H2, and rust is similar to normal Fischer Tropsch catalyst. My costs would be low, and I’d expected to get better conversion since I should get fewer low molecular weight products like methane, ethane and methanol. Everything fundamental looked like it was in my favor.

With all the fundamentals in place, I figured my only problem would be to design a reasonably cheap reactor. At first I considered a fluidized bed reactor, but decided on a packed bed reactor instead, 8″ long by 3/4″ OD. This was a tube, filled with wood chips and iron oxide as a catalyst. I introduced high pressure hydrogen via a 150 psi hydrogen + 5% He mix. I hoped to see gasoline and water come out the other end. (I had the hydrogen – helium mix left over from a previous experiment, and was paying rental; otherwise I would have used pure hydrogen). I used heat tape and a controller to keep the temperature near-constant.

Controlling the temperature was key, I thought, to my aim of avoiding dehydration and the formation of new carbon-carbon bonds. At too high a temperature, the cellulose molecules would combine and lose water to form a brown high molecular weight tar called bio-oil, as well as methane and char. Bio-oil is formed the same way you form caramel from sugar, and as with sugar, it’s nothing you’d want to put in a car. If I operated at too low a temperature (or with the wrong catalyst) the reaction would be too slow, and the capital costs would be excessive. I could keep the temperature in the right (Goldilocks) temperature, I thought with the right catalyst and the right (high) hydrogen pressure.

No matter how I did this, I knew that I’d get some carbon-carbon bond formation, and perhaps a little char, but so long as it wasn’t too much it should be manageable. I figured I could hydrogenate the tar and remove the char at the end of the process. Most of the gasoline energy would come from the trees, and not the hydrogen, and there would be little hydrogen wasted forming methane. Trees would always be cheap: they grow quickly, and are great at capturing solar energy. Many cities pay for disposal of their tree waste, so perhaps a city would pay us to take their wood chips. With cheap wood, the economics would be good so long as used all the hydrogen I put in, and got some reasonable fraction of energy from the wood. 

i began my reaction at 150°C with 50 psi hydrogen. At these conditions, I saw no reaction; I then raised the temperature to 200°C, then raised the pressure to 100 psi (still nothing) and then tried 250°C, still at 100psi. By now we were producing water but it was impossible to tell if we were hydrogenating the cellulose to gasoline, or dehydrating the cellulose to bio-oil.

As it turned out we were getting something worse that bio-oil: bio-oil gunk. Instead of the nasty brown liquid that’s made when wood is cooked to dehydration (water removal, caramelization), I got something that was nastier than I’d imagined possible. The wood molecules did not form nice chains but combined to form acidic, aromatic gunk (aromatic in both senses: benzine-type molecules and smelly) that still contained unreacted wood as a sort of press-board. The gunk was corrosive and reactive; it probably contained phenol, and seemed bent on reacting to form a phenolic glue. I found the gunk was insoluble in most everything: water, gasoline, oil, methanol (the only exception was ethanol). As best I can tell, you can not react this gunk with hydrogen to make gasoline as it is non-volatile, and almost impossible to get out of my clogged reactor. Perhaps a fluidized bed would be would be better, but I’m afraid it would form wood clumps even there. 

I plan to try again, perhaps using higher pressure hydrogen and perhaps a liquid hydrogen carrier, to get the hydrogen to the core of the wood and speed the catalysis of the desired products. The key is finding a carrier that is not too expensive or that can be easily recovered.

Robert E. Buxbaum, Dec 13, 2013. Here’s something on a visit to my lab, on adding hydrogen to automobile engines, and on the right way to do science. And here’s my calculation for how much wood a woodchuck chucks if a woodchuck could chuck wood, (100 lbs/ night) plus why woodchucks do not chuck wood like beavers.

Simple electroplating of noble metals

2 Replies
Electro-coating gold onto a Pd tube by dissolving an iron wire.

Electro-coating gold onto at Pd-coated tube by dissolving an iron wire at REB Research.

Here’s a simple trick for electroplating noble metals: gold, silver, copper, platinum. I learned this trick at Brooklyn Technical High School some years ago, and I still use it at REB Research as part of our process to make hydrogen permeation barriers, and sulfur tolerant permeation membranes.  It’s best used to coat reasonably inactive, small objects,  e.g. to coat copper on a nickel or silver on a penny for a science fair.

As a first step, you make a dilute acidic solution of the desired noble metal. Dissolve a gram or so of copper sulphate, silver nitrate, or gold chloride per 250 ml of water. Make sure the solution is acidic using pH paper, add acid if needed aiming for a pH of 3 to 4. Place some solution into a test tube or beaker of a size that will hold the object you want to coat. As a next step, attach an iron or steel wire to the object, I typically use bailing wire from the hardware store wrapped several times about the top of the object, and run the length of the object; see figure. Place the object into your solution and wait for 5 to 30 minutes. Coating works without the need for any other electric source or any current control.

The iron wire creates the electricity used in electroplating the noble metal. Iron has a higher electro-motive potential than hydrogen and hydrogen has a higher potential than the noble metals. In acid solution, the iron wire dissolves but (it’s hoped) the substrate does not. Each iron atom gives up two electrons, becoming Fe++. Some of these electrons go on to reduce hydrogen ions making H2 (2H+ + 2e– –> H2), but most should go to reduce the noble metal ions in the solution to form a coat of metallic gold, silver, or copper on both the wire and the object. See an example of how I do calculations regarding voltage, electron number, and Gibbs free energy.

Transferring electrons requires you have good electrical contact between the wire and the object. Most of the noble metal coats the object, not the wire since the object is bigger, typically. Thanks to my teachers at Brooklyn Technical High School for teaching me. For a uniform coat, it helps to run the wire down parallel to the entire length of tube; I think this is a capacitance, field effect. For a larger object, you may want several wires if you are plating a larger object. For a thicker coat, I found you are best off making many thin coats and heating them. This reduces tension forces in the coat, I think.

The picture shows a step in the process we use making our sulfur-resistant hydrogen permeation membranes (buy them here), used, e.g. to concentrate impurities in a hydrogen stream for improved gas chromatography. The next step is to dissolve the gold or copper into the palladium.

Go here for a great periodic table cup from REB Research, or for the rest of our REB Research products. I occasionally make silver-coated pennies for schoolchildren, but otherwise use this technology only for in-house production.

R.E. Buxbaum, July 20, 2013.

Thermodynamics of hydrogen generation

7 Replies

Perhaps the simplest way to make hydrogen is by electrolysis: you run some current through water with a little sulfuric acid or KOH added, and for every two electrons transferred, you get a molecule of hydrogen from one electrode and half a molecule of oxygen from the other.

2 OH- –> 2e- + 1/2 O2 +H2O

2H2O + 2e- –>  H2 + 2OH-

The ratio between amps, seconds and mols of electrons (or hydrogen) is called the Faraday constant, F = 96500; 96500 amp-seconds transfers a mol of electrons. For hydrogen production, you need 2 mols of electrons for each mol of hydrogen, n= 2, so

it = 2F where and i is the current in amps, and t is the time in seconds and n is the number electrons per molecule of desired product. For hydrogen, t = 96500*2/i; in general, t = Fn/i.

96500 is a large number, and it takes a fair amount of time to make any substantial amount of hydrogen by electrolysis. At 1 amp, it takes 96500*2 = 193000 seconds, 2 days, to generate one mol of hydrogen (that’s 2 grams H2 or 22.4 liters, enough to fill a garment bag). We can reduce the time by using a higher current, but there are limits. At 25 amps, the maximum current of you can carry with house wiring it takes 2.14 hours to generate 2 grams. (You’ll have to rectify your electricity to DC or you’ll get a nasty H2 /O2 mix called Brown’s gas, While normal H2 isn’t that dangerous, Browns gas is a mix of H2 and O2 and is quite explosive. Here’s an essay I wrote on separating Browns gas).

Electrolysis takes a fair amount of electric energy too; the minimum energy needed to make hydrogen at a given temperature and pressure is called the reversible energy, or the Gibbs free energy ∆G of the reaction. ∆G = ∆H -T∆S, that is, ∆G equals the heat of hydrogen production ∆H – minus an entropy effect, T∆S. Since energy is the product of voltage current and time, Vit = ∆G, where ∆G is the Gibbs free energy measured in Joules and V,i, and t are measured Volts, Amps, and seconds respectively.

Since it = nF, we can rewrite the relationship as: V =∆G/nF for a process that has no energy losses, a reversible process. This is the form found in most thermodynamics textbooks; the value of V calculated this way is the minimum voltage to generate hydrogen, and the maximum voltage you could get in a fuel cell putting water back together.

To calculate this voltage, and the power requirements to make hydrogen, we use the Gibbs free energy for water formation found in Wikipedia, copied below (in my day, we used the CRC Handbook of Chemistry and Physics or a table in out P-chem book). You’ll notice that there are two different values for ∆G depending on whether the water is a gas or a liquid, and you’ll notice a small zero at the upper right (∆G°). This shows that the values are for an imaginary standard state: 20°C and 1 atm pressure. You can’t get 1 atm steam at 20°C, it’s an extrapolation; behavior at typical temperatures, 40°C and above is similar but not identical. I’ll leave it to a reader to send this voltage as a comment.

Liquid H2O formation ∆G° = -237.14
Gaseous H2O formation ∆G° = -228.61

The reversible voltage for creating liquid water in a reversible fuel cell is found to be -237,140/(2 x 96,500) = -1.23V. We find that 1.23 Volts is about the minimum voltage you need to do electrolysis at 0°C because you need liquid water to carry the current; -1.18 V is about the maximum voltage you can get in a fuel cell because they operate at higher temperature with oxygen pressures significantly below 1 atm. (typically). The minus sign is kept for accounting; it differentiates the power out case (fuel cells) from power in (electrolysis). It is typical to find that fuel cells operate at lower voltages, between about .5V and 1.0V depending on the fuel cell and the power load.

Most electrolysis is done at voltages above about 1.48 V. Just as fuel cells always give off heat (they are exothermic), electrolysis will absorb heat if run reversibly. That is, electrolysis can act as a refrigerator if run reversibly. but electrolysis is not a very good refrigerator (the refrigerator ability is tied up in the entropy term mentioned above). To do electrolysis at reasonably fast rates, people give up on refrigeration (sucking heat from the environment) and provide all the entropy needed for electrolysis in the electricity they supply. This is to say, they operate at V’ were nFV’ ≥ ∆H, the enthalpy of water formation. Since ∆H is greater than ∆G, V’ the voltage for electrolysis is higher than V. Based on the enthalpy of liquid water formation,  −285.8 kJ/mol we find V’ = 1.48 V at zero degrees. The figure below shows that, for any reasonably fast rate of hydrogen production, operation must be at 1.48V or above.

Electrolyzer performance; C-Pt catalyst on a thin, nafion membrane

Electrolyzer performance; C-Pt catalyst on a thin, nafion membrane

If you figure out the energy that this voltage and amperage represents (shown below) you’re likely to come to a conclusion I came to several years ago: that it’s far better to generate large amounts of hydrogen chemically, ideally from membrane reactors like my company makes.

The electric power to make each 2 grams of hydrogen at 1.5 volts is 1.5 V x 193000 Amp-s = 289,500 J = .080 kWh’s, or 0.9¢ at current rates, but filling a car takes 20 kg, or 10,000 times as much. That’s 800 kW-hr, or $90 at current rates. The electricity is twice as expensive as current gasoline and the infrastructure cost is staggering too: a station that fuels ten cars per hour would require 8 MW, far more power than any normal distributor could provide.

By contrast, methanol costs about 2/3 as much as gasoline, and it’s easy to deliver many giga-joules of methanol energy to a gas station by truck. Our company’s membrane reactor hydrogen generators would convert methanol-water to hydrogen efficiently by the reaction CH3OH + H2O –> 3H2 + CO2. This is not to say that electrolysis isn’t worthwhile for lower demand applications: see, e.g.: gas chromatography, and electric generator cooling. Here’s how membrane reactors work.

R. E. Buxbaum July 1, 2013; Those who want to show off, should post the temperature and pressure corrections to my calculations for the reversible voltage of typical fuel cells and electrolysis.