Tag Archives: gasoline

Hydrogenation, how we’ve already entered the hydrogen economy

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The hydrogen economy is generally thought to come in some distant future, where your car (and perhaps your home) runs on hydrogen, and the hydrogen, presumably, is made by clean nuclear or renewable solar or wind power. This is understood to be better than the current state of things where your car runs on dirty gasoline, and your home runs on coal or gas, except when the sun is shining bright and the wind is blowing hard. Our homes and cars can not run on solar or wind alone, although solar cells have become quite cheap, because solar power is only available in the daytime, basically for 6 hours, from about 9AM to 3PM. Hydrogen has been proposed as a good way to store solar and wind energy that you can’t use, but it’s not easy to store hydrogen — or is it? I’d like to suggest that, to a decent extent, we already store green hydrogen and use it to run our trucks. We store this hydrogen in the form of Diesel fuel, so you don’t realize it’s hydrogen.

Much of the oil in the United States these days comes from tar sands and shale. It doesn’t flow well at room temperature, and is too heavy and gooey for normal use. We could distill this crude oil and use only the light parts, but that would involve throwing away a huge majority of the oil. Instead we steam reform it to gasoline, ethylene and other products. The reaction is something like this, presuming an input feed of naphtha, C10H8:

C10H8 + 2 H2O –> C7H8 + C2H4 + CO2.

The C2H4 component is ethylene. We use it to make plastics. The C7H8 is called toluene. It is a component of high octane gasoline (octane rating about 114). The inventor of the process, Eugene Jules Houdry claimed to have won WWII for the allies because his secret process (Houdryflow catalytic cracking) allowed high production of lots of gasoline of very high octane, giving US and British planes and trucks higher mpg than the Germans or Japanese had. It was a great money maker, but companies can make even more by adding hydrogen.

Schematic of the hydrocracking process, from the US energy information agency

Over the last 2-3 decades, refineries have been adding catalytic hydrogenation processes. These convert high octane aromatic products, like toluene to low -octane diesel and jet fuel. These products sell for more. Aromatic toluene is exposed to hydrogen at about 500°C and 300 psi (20 bar) to produce heptane, an excellent diesel fuel with about 7% more energy content than toluene per gallon.

C7H8 + 4H2 –> C7H16.

Diesel fuel sell for about 20% more than gasoline per gallon, in part because of the higher energy content, and because Diesel engines are more efficient than gas engines. What’s more, toluene expands as it’s converted to heptane. One gallon of toluene converts to 1.16 gallons of heptane. As a result hydrogenation adds about 40% to the sales price per molecule. Refineries have found that they can make significant money this way if they can buy cheap hydrogen. Over the last few years, several refineries in Norway and Texas (high sun and wind areas) have added hydrogenators along with electrolysis units to produce the cheap hydrogen when no one needs the unwanted electricity generated when supply exceeds demand. Here is an analysis of the thermodynamics of this type of hydrogen generation.

Robert Buxbaum, May 11, 2023

Alcohol and gasoline don’t mix in the cold

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One of the worst ideas to come out of the Iowa caucuses, I thought, was Ted Cruz claiming he’d allow farmers to blend as much alcohol into their gasoline as they liked. While this may have sounded good in Iowa, and while it’s consistent with his non-regulation theme, it’s horribly bad engineering.

At low temperatures ethanol and gasoline are no longer quite miscible

Ethanol and gasoline are that miscible at temperatures below freezing, 0°C. The tendency is greater if the ethanol is wet or the gasoline contains benzenes

We add alcohol to gasoline, not to save money, mostly, but so that farmers will produce excess so we’ll have secure food for wartime or famine — or so I understand it. But the government only allows 10% alcohol in the blend because alcohol and gasoline don’t mix well when it’s cold. You may notice, even with the 10% mixture we use, that your car starts poorly on the coldest winter days. The engine turns over and almost catches, but dies. A major reason is that the alcohol separates from the rest of the gasoline. The concentrated alcohol layer screws up combustion because alcohol doesn’t burn all that well. With Cruz’s higher alcohol allowance, you’d get separation more often, at temperatures as high as 13°C (55°F) for a 65 mol percent mix, see chart at right. Things get worse yet if the gasoline gets wet, or contains benzene. Gasoline blending is complex stuff: something the average joe should not do.

Solubility of dry alcohol (ethanol) in gasoline. The solubility is worse at low temperature and if the gasoline is wet or aromatic.

Solubility of alcohol (ethanol) in gasoline; an extrapolation based on the data above.

To estimate the separation temperature of our normal, 10% alcohol-gasoline mix, I extended the data from the chart above using linear regression. From thermodynamics, I extrapolated ln-concentration vs 1/T, and found that a 10% by volume mix (5% mol fraction alcohol) will separate at about -40°F. Chances are, you won’t see that temperature this winter (and if you you do, try to find a gas mix that has no alcohol. Another thought, add hydrogen or other combustible gas to get the engine going.

Robert E. Buxbaum, February 10, 2016. Two more thoughts: 1) Thermodynamics is a beautiful subject to learn, and (2) Avoid people who stick to foolish consistency. Too much regulation is bad, as is too little: it’s a common pattern: The difference between a cure and a poison is often just the dose.

Michigan’s road bill — why not?

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Stagnating before the Michigan Senate is a road improvement bill that passed the Michigan house 10 days ago. Though it’s not great, I hope they sign the bill. The bill would raise raise $600 million to $1.2 billion/year, an increase of $60 to $120 per person per year ratcheting up over the next six years. The first stage of the bill would take effect in October 2016, and would raise $400 million by increasing our car/ truck registration fees by about 40%. People with normal sedans would pay about $60 more per car per year. Those with more expensive, heavier vehicles would pay more. Though our registration fee is already among the highest in the nation, raising it further has the potential (It seems to me) to be the most fair and reasonable source of additional revenue. People with fancy cars, I imagine, are wealthy and those with heavy cars (I imagine) do the most road damage. This is the part of the bill that has proven the most contentious.

The next stage would begin in early 2018. It would raise $200 million by increasing Michigan diesel and gasoline taxes. The larger part would be on diesel fuel, an increase of 7.3 cents/gal presumably to soak out-of-state truckers who come through Michigan. These individuals deserve extra taxation, I imagine, because they don’t pay registration fees and probably damage our roads even more than those with fancy cars. Besides, they don’t vote in Michigan. The gas tax increase is smaller, 3.3 cents/ gal on regular gas, but Democrats are correct to point out that it is regressive. It takes a greater fraction from the poorer than from the rich. The hope is that, by the time the tax increase takes effect, we’ll have some inflation and also some more fuel-efficient cars so the bite won’t be as bad. Sorry to say, we already pay the 10th highest gas tax in the country.

The final phase of the road funding bill would not take full effect until 2021. The idea is to transfer $600 million from the general fund to pay for the roads with money left over to reduce home-owner taxes. Underlying the ability to do this is an assumption that Michigan industry and home prices will recover enough between now and then that we’ll be able to stop using the gasoline taxes to fund our schools, ideally with money left over from the regular income and sales tax. While I’d like to see this happen, and while this is possible given that the last few years have seen the state’s GDP recover at a 15.5+% growth rate (third highest in the nation) there is also a basis to say the assumptions are over- optimistic. On the other hand, the Democratic plan, based on 1.6% growth next year is likely over-pessimistic. As The Yogi says, “Predictions are always difficult, especially about the future.”

Whatever your views of the future, our roads are crumbling now, and new money is needed to fix them now before they get worse. If taxes must be raised, I’m inclined to do it with use -taxes, that is by charging those who use the services most. This is a philosophical preference of mine. Not all Republicans agree with this, and only one House Democrat has signed on so far. It was the view of the old-time, labor Democrats I grew up with, but not of today’s Democrats who prefer to tax “the rich” for any and all goods and services. Their point: that there are struggling, poor people who drive heavy, expensive cars. They’ve something of a point on the heavy cars, but I have less sympathy for the rest. I wrote a comic story about a poor guy trying to dispose of an expensive car, a Viper. My guess is that struggling rappers and poser politicians would not find it funny.

Dollars per capita spent on roads, 2013. From MDoT's road funding proposal.

Dollars per capita spent on roads, 2013. From MDoT’s road funding proposal.

Part of the way that MDoT (the Michigan Department of Transportation) justified its target of $600 million to $1.2 billion was by comparison with surrounding states — not my favorite way of analysis. The MDoT graphic shows that Michiganians spend about $57 less per capita on roads than folks in Illinois, Wisconsin, or Ohio, and about $100 less than folks in Indiana or Pennsylvania. Multiply $57 by our state’s population, 10 million, and they conclude we should spend some $570 million more per year. Multiply by $100, and you get $1.0 billion.

While the need for at least $600 million/year sounds about right, I note that the per-capita spending justification seems dubious. If you calculate instead on the basis of dollars per lane-mile, as below, you find that Michiganians are already paying more per mile than Minnesota, Wisconsin, or Indiana. You’ll also note that Ohio and Illinois pays about 1 1/2 times as much their roads aren’t much better. A major part of the variation, I suspect, is corruption, and the rest, I guess is incompetence. Illinois, perhaps the most corrupt state in the mid-west, has seen 4 of its past 5 governors go to jail, along with innumerable Chicago Aldermen and lesser officials. Citizens of Illinois pay for this corruption in over-size construction projects, and over-size construction fees. After the $600 million increase, we’ll pay $8,950 per lane mile suggesting we are still not quite as costly per lan-mile as Illinois or Ohio. If it turns out we need the full $1.2 billion extra, it will suggest we are even more incompetent or corrupt than Illinois.

Road funding state by state comparison.

Road funding state by state comparison, from the same MDoT report, 2013.

An ideal way I’d like to reduce the costs of Michigan’s roads would be to reduce corruption, a trend that’s already helped to revitalize Detroit since the Justice department jailed the mayor and his father plus some associates for “pay for play”. I’m sure it also helped to remove the chief of police (millions in his ceiling) and Bobby Ferguson of the useless, expensive Jail project and Guardian building scandal.

Conviceted IL

It’s somewhat hard to judge the level of general incompetence in a state, and even harder to find a fix. Minnesota had a bridge collapse in 2007, and we had the Zilwaukee in 1982 (and 2008), the 9 mile bridge collapse of 2009, and the Southfield overpass collapse of 2014. It’s been proposed that we should be able to fix both our corruption and our incompetence problems by holding the contractors responsible for any failures. If only it were that easy. Holding contractors responsible might get some contractors to allow the concrete cure for longer periods under water before opening a road, but I’m not sure the public would stand for it. A more-likely outcome is that crooked contractors would charge more for the same bad work, and then go bankrupt as soon as the road fails. If their company were appropriately structured, they could re-appear the next day: the same people and equipment, operating under a new corporate name.

The biggest single incompetence issue that I can see appears to be poor under-road drainage. In Oakland county, where I am, the drain department looks responsible for the major flood of last summer. We’ve had rains this big in previous years without this massive flooding. I suspect a lack of dry-wells, but don’t know. From what I see, the drainage is bad beneath many Oakland roads, too. It seems like the concrete slabs are not deteriorating as much as they are coming apart. That’s a sign of bad drainage. I also see sink-holes, new lakes, and places where the sidewalks sink. Again, that’s a sign of bad drainage; a sign there is a swamp near or beneath the road. If the ground below a major road is a swamp, there is no practical way a contractor can build a long-lasting road over it. Until the drains get better, or the corruption subsides, we’re going to have to replace the roads often at a cost of another $600 million/year. We might as well acknowledge our problems and sign the bill.

Robert Buxbaum, November 2-3, 2015. If you feel like getting involved, contact your state senator and tell him/her to vote yes (or no). Our senator is Vince Gregory. And if anyone would like to put me on a drainage board, I’d be happy to serve for free.

My latest invention: improved fuel cell reformer

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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.