Tag Archives: Chemical engineering

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

My home-made brandy and still.

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MY home-made still, and messy lab. Note the masking tape seal and the nylon hoses. Nylon is cheaper than copper. The yellow item behind the burner is the cooling water circulation pump. The wire at top and left is the thermocouple.

I have an apple tree, a peach tree, and some grape vines. They’re not big trees, but they give too much fruit to eat. The squirrels get some, and we give some away. As for the rest, I began making wine and apple jack a few years back, but there’s still more fruit than I can use. Being a chemical engineer, I decided to make brandy this year, so far only with pears and apples.

The first steps were the simplest: I collected fruit in a 5 gallon, Ace bucket, and mashed it using a 2×4. I then added some sugar and water and some yeast and let it sit with a cover for a week or two. Bread yeast worked fine for this, and gives a warm flavor, IMHO. A week or so later, I put the mush into a press I had fro grapes, shown below, and extracted the fermented juice. I used a cheesecloth bag with one squeezing, no bag with the other. The bag helped, making cleanup easier.

The fruit press, used to extract liquid. A cheese cloth bag helps.

I did a second fermentation with both batches of fermented mash. This was done in a pot over a hot-plate on warm. I added more sugar and some more yeast and let it ferment for a few more days at about 78°F. To avoid bad yeasts, I washed out the pot and the ace bucket with dilute iodine before using them– I have lots of dilute iodine around from the COVID years. The product went into the aluminum “corn-cooker” shown above, 5 or 6 gallon size, that serves as the still boiler. The aluminum cover of the pot was drilled with a 1″ hole; I then screwed in a 10″ length of 3/4″ galvanized pipe, added a reducing elbow, and screwed that into a flat-plate heat exchanger, shown below. The heat exchanger serves as the condenser, while the 3/4″ pipe is like the cap on a moonshiner still. Its purpose is to keep the foam and splatter from getting in the condenser.

I put the pot on the propane burner stand shown, sealed the lid with masking tape (it worked better than duct tape), hooked up the heat exchanger to a water flow, and started cooking. If you don’t feel like making a still this way, you can buy one at Home Depot for about $150. Whatever route you go, get a good heat exchanger/ condenser. The one on the Home-depot still looks awful. You need to be able to take heat out as fast as the fire puts heat in, and you’ll need minimal pressure drop or the lid won’t seal. The Home Depot still has too little area and too much back-pressure, IMHO. Also, get a good thermometer and put it in the head-space of the pot. I used a thermocouple. Temperature is the only reasonable way to keep track of the progress and avoid toxic distillate.

A flat-plate heat exchanger, used as a condenser.

The extra weight of the heat exchanger and pipe helps hold the lid down, by the way, but it would not be enough if there was a lot of back pressure in the heat exchanger-condenser. If your lid doesn’t seal, you’ll lose your product. If you have problems, get a better heat exchanger. I made sure that the distillate flows down as it condenses. Up-flow adds back pressure and reduces condenser efficiency. I cooled the condenser with water circulated to a bucket with the cooling water flowing up, counter current to the distillate flow. I could have used tap water via a hose with proper fittings for cooling, but was afraid of major leaks all over the floor.

With the system shown, and the propane on high, it took about 20 minutes to raise the temperature to near boiling. To avoid splatter, I turned down the heater as the temperature approached 150°F. The first distillate came out at 165°F, a temperature that indicated it was not alcohol or anything you’d want to drink. I threw away the first 2-3 oz of this product. You can sniff or sip a tiny amount to convince yourself that this this is really nasty, acetone, I suspect, plus ethyl acetate, and maybe some ether and methanol. Throw it away!

After the first 2-3 ounces, I collected everything to 211°F. Product started coming in earnest at about 172°F. I ended distillation at 211°F when I’d collected nearly 3 quarts. For my first run, my electronic thermometer was off and I stopped too early — you need a good thermometer. The material I collected and was OK in taste, especially when diluted a bit. To test the strength, I set some on fire, the classic “100% proof test”, and diluted till it to about 70% beyond. This is 70% proof, by the classic method. I also tried a refractometer, comparing the results to whiskey. I was aiming for 60-80 proof (30-40%).

My 1 gallon aging barrel.

I tried distilling a second time to improve the flavor. The result was stronger, but much worse tasting with a loss of fruit flavor. By contrast, a much better resulted from putting some distillate (one pass) in an oak barrel we had used for wine. Just one day in the barrel helped a lot. I’ve also seen success putting charred wood cubes set into a glass bottle of distillate. Note: my barrel, as purchased, had leaks. I sealed them with wood glue before use.

I only looked up distilling law after my runs. It varies state to state. In Michigan, making spirits for consumption, either 1 gal or 60,000 gal/year, requires a “Distilling, Rectifying, Blending and/or Bottling Spirits” Permit, from the ATF Tax and Trade Bureau (“TTB”) plus a Small Distiller license from Michigan. Based on the sale of stills at Home Depot and a call to the ATF, it appears there is little interest in pursuing home distillers who do not sell, despite the activity being illegal. This appears similar to state of affairs with personal use marijuana growers in the state. Your state’s laws may be different, and your revenuers may be more enthusiastic. If you decide to distill, here’s some music, the Dukes of Hazard theme song.

Robert Buxbaum, November 23, 2022.

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.

Chemical engineers and boilers, ‘I do anything’

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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.

Chemist v Chemical Engineer joke

What’s the difference between a chemist and a chemical engineer?

 

How much they make.

 

I made up this joke up as there were no other chemical engineer jokes I knew. It’s an OK double entente that’s pretty true — both in terms of product produced and the amount of salary (there’s probably a cause-and-effect relation here). Typical of these puns, this joke ignores the internal differences in methodologies and background (see my post, How is Chemical engineering?). If you like, here’s another engineering joke,  a chemistry joke, and a dwarf joke.

R.E. Buxbaum –  June 28, 2013.

How is Chemical Engineering?

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I’m sometimes asked about chemical engineering by high-schoolers with some science aptitude. Typically they are trying to decide between a major in chemistry or chemical engineering. They’ve typically figured out that chemical engineering must be some practical version of chemistry, but can’t quite figure out how that could be engineering. My key answer here is: unit operations.

If I were a chemist trying to make an interesting product, beer or whisky say, I might start with sugar, barley, water and yeast, plus perhaps some hops and tablets of nutrients and antimicrobial. After a few hours of work, I’d have 5 gallons of beer fermenting, and after a month I’d have beer that I could either drink or batch-distill into whisky. If I ran the cost numbers, I’d find that my supplies cost as much to make as buying the product in a store; the value of my time was thus zero and would not be any higher if I were to scale up production: I’m a chemist.

The key to making my time more valuable is unit operations. I need to scale up production and use less costly materials. Corn costs less than sugar but has to be enzyme processed into a form that can be fermented. Essentially, I have to cook a large batch of corn at the right temperatures (near boiling) and then add enzymes from the beer or from sprouted corn and then hold the temperature for an hour or more. Sounds simple, but requires good heat control, good heating, and good mixing, otherwise the enzymes will die or won’t work or the corn will burn and stick to the bottom of the pot. These are all unit operations; you’ll learn more about them in chemical engineering.

Reactor design is a classical unit operation. Do I react in large batches, or in a continuous fermentor. How do I hold on to the catalyst (enzymes); what is the contact time; these are the issues of reactor engineering, and while different catalysts and reactions have different properties and rates, the analysis is more-or-less the same.

Another issue is solid-liquid separation, in this case filtration of the dregs. When made in small batches, the bottoms of the beer barrel, the dregs, were let to settle and then washed down the sink. At larger scales, settling will take too long and will still leave a beer that is cloudy. Further, the dregs are too valuable to waste. At larger scales, you’ll want to filter the beer and will want to do something to the residue. Centrifugal filtration is typically used and the residue is typically dried and sold as animal feed. Centrifugal filtration is another unit operation.

Distillation is another classical unit operation. An important part here is avoiding hangover-producing higher alcohols and nasty tasting, “fusel oils.” There are tricks here that are more-or-less worth doing depending on the product you want. Typically, you start with a simple processes and equipment and keep tweaking them until the product and costs are want you want. At the end, typically, the process equipment looks more like a refinery than like a kitchen: chemical engineering equipment is fairly different from the small batch equipment that was used as the chemist.

The same approach to making things and scaling them up also applied in management situations, by the way, and many of my chemical engineering friends have become managers.