UD catalyst can convert CO2 to CO with 92 percent efficiency
A team of researchers at the University of Delaware has developed a highly selective catalyst capable of electrochemically converting carbon dioxide — a greenhouse gas — to carbon monoxide with 92 percent efficiency. The carbon monoxide then can be used to develop useful chemicals.
The researchers recently reported their findings in Nature Communications.
“Converting carbon dioxide to useful chemicals in a selective and efficient way remains a major challenge in renewable and sustainable energy research,” according to Feng Jiao, assistant professor of chemical and biomolecular engineering and the project’s lead researcher.
Co-authors on the paper include Qi Lu, a postdoctoral fellow, and Jonathan Rosen, a graduate student, working with Jiao.
The researchers found that when they used a nano-porous silver electrocatalyst, it was 3,000 times more active than polycrystalline silver, a catalyst commonly used in converting carbon dioxide to useful chemicals.
Silver is considered a promising material for a carbon dioxide reduction catalyst because of it offers high selectivity — approximately 81 percent — and because it costs much less than other precious metal catalysts. Additionally, because it is inorganic, silver remains more stable under harsh catalytic environments.
The exceptionally high activity, Jiao said, is likely due to the UD-developed electrocatalyst’s extremely large and highly curved internal surface, which is approximately 150 times larger and 20 times intrinsically more active than polycrystalline silver.
Jiao explained that the active sites on the curved internal surface required a much smaller than expected voltage to overcome the activation energy barrier needed drive the reaction.
The resulting carbon monoxide, he continued, can be used as an industry feedstock for producing synthetic fuels, while reducing industrial carbon dioxide emissions by as much as 40 percent.
To validate whether their findings were unique, the researchers compared the UD-developed nano-porous silver catalyst with other potential carbon dioxide electrocatalysts including polycrystalline silver and other silver nanostructures such as nanoparticles and nanowires.
Testing under identical conditions confirmed the non-porous silver catalyst’s significant advantages over other silver catalysts in water environments.
Reducing greenhouse carbon dioxide emissions from fossil fuel use is considered critical for human society. Over the last 20 years, electrocatalytic carbon dioxide reduction has attracted attention because of the ability to use electricity from renewable energy sources such as wind, solar and wave.
Ideally, Jiao said, one would like to convert carbon dioxide produced in power plants, refineries and petrochemical plants to fuels or other chemicals through renewable energy use.
A 2007 Intergovernmental Panel on Climate Change report stated that 19 percent of greenhouse gas emissions resulted from industry in 2004, according to the Environmental Protection Agency’s website.
“Selective conversion of carbon dioxide to carbon monoxide is a promising route for clean energy but it is a technically difficult process to accomplish,” said Jiao. “We’re hopeful that the catalyst we’ve developed can pave the way toward future advances in this area.”
The research team’s work is supported through funding from the American Chemical Society Petroleum Research Fund and University of Delaware Research Foundation. Jiao has patented the novel application technique in collaboration with UD’s Office of Economic Innovation and Partnerships.
Oh great. Spend lots of money turning plant food into something that kills people.
Warning – Idiots at work
On first reading, I thought that by pointing out that CO2 is a greenhouse gas, they were implying that this conversion could be a way to fight global warming. Of course, the amount of CO2 thus converted could never be more than a negligible portion of the total atmospheric CO2.
So, if you expend 100% of the energy obtained from burning fossil fuels on a catalytic process with 92% efficiency, you can have 0 energy and 60% of the original carbon dioxide emissions.
Warmists will love this.
Oh yes, poison gas is very useful. If, you know, you’re a mass murderer.
Also, no matter how efficient, it basically is unburning carbon. Which requires that you give back the energy you got burning it. Which makes the burning itself highly INefficient. It takes a harmless gas and makes an extremely poisonous one. Converting the CO into fuel makes little sense as that requires still more energy, and of course the fuel burned to make the energy (or the energy obtained from renewable sources to make the fuel) would be better used directly. About the only point I can see to this is making OTHER stuff for which CO is a useful feedstock and for which it is more expensive to separate out CO from e.g. burning charcoal or coal than it is to convert all/most of the mix of CO and CO_2 into CO.
That is, it may be very useful to organic chemists. It is not news or useful in the “things to do with gigatons of CO_2/year” category.
rgb
@all and everyone including Anthony Watts
Synthetic fuels is also what I believe in, but it takes input energy. CO + 1/2O2->CO2 is quite a hot process. You can drive car by it.
CO +H2O -CO2 + H2, beat that, and CO2 back in the process….
But what about (CO2 + H2O)n & n h.ny-> (HCOH)n , where h .ny can be solar energy.
You will need a biological catalyst for it , a green one,…
Proper (HCOH)n can be brewed into beers, but I heard from over there that they rather take and press apples, that are then boubbled. And the result is set out in the fields under chill conditions of the kind that you had quite recently. Most of it will freeze, but you can drive cars on the content of it that will not freeze.
The abstract doesn’t talk about the energy requirements. Heck, it could be a perpetual motion process. Bun the fuel, convert CO2 to CO, redirect it back to the combustion process, burn it, convert the resultant CO2 to CO…
Landfill gas is ~35% CO2, what an energy source.
Sounds interesting, but I’d like to see more details.
I think the voltage involved in the conversion is fairly modest. Catalysts do have the ability to leverage small inputs, and some do not require external energy at all.
The real issue is: How expensive is this technology, and is the resulting CO accessible and processable on an economic basis? It might actually be a net gain.
In fact, if it IS a net gain, I’d expect our catastrophist friends to come out against it — because it means that fossil fuel powerplants could continue. Such an improvement does not accomplish the stated goal of “de-industrializing” society. In their minds, it seems, if we could continue to have abundant energy we would not be sufficiently punished.
===|==============/ Keith DeHavelle
They have a very nice result from the perspective of chemistry and catalysis. No one should deny that.
But look, converting CO2 to CO requires energy. In their case, they’re doing electrocatalysis, which means driving the reaction with an applied low voltage (-0.6 V). Two electrons are used up for every CO2 that becomes a CO. In short, electricity is needed.
They get 92% efficiency, which is amazingly good and also means they have to put 1.09 electrons in to get 1 electron out. The process, as usual, goes with net energy loss. As it *must* do because the reaction is going thermodynamically uphill.
In other words, they’ll need a power plant to produce CO from CO2. They won’t get as much energy back out as they put in. Even if the power plant uses natural gas, they’ll produce more CO2 providing the electricity for the reaction, than the CO2-to-CO process will remove.
So long as fossil fuels are available, their process CO will never be economically worthwhile as a feed gas.
The whole publicity cachet of the article revolves around the bankruptcy of carbon capture. The chemistry is great. The catalysis is excellent. The researchers are to be congratulated. If someone tries to promote it for carbon capture, it’ll be a money rat-hole. The press release is all sustainability posery.
I would suggest doing it in a closed garage and preferably in State College, PA.
rgbatduke says: “Also, no matter how efficient, it basically is unburning carbon. Which requires that you give back the energy you got burning it. Which makes the burning itself highly INefficient. It takes a harmless gas and makes an extremely poisonous one….”
Does this mean there’s going to be a new 10-10 video?
With nuclear as the power source, “The resulting carbon monoxide, he continued, can be used as an industry feedstock for producing synthetic fuels”
So much for Peak Oil.
So with Thorium reactors and this chemistry, problem solved. :>)
Someone ring up Obama and then we can all go home.
Anth0ny:
The suggested process is expensive and pointless.
It would be much better to obtain CO from coal using a water gas shift.
The shift can also provide hydrogen which is also useful as in input to manufacture of synthetic hydrocarbons. It is simply, accurately and clearly explained by wicki here.
Water gas is rich in nitrogen if coal is burned in air to provide the needed energy. This is overcome by external heating or burning coal in pure oxygen as the heat supply.
The process was invented in 1780 and has been conducted at commercial scale first in 1828.
Richard
If this can be engineered as a small-scale process, could it provide a means of local storage of intermittent wind/solar energy? How would it compare with straight electrolysis?
@ all and everyone
Yes really very fine, a lot of it, and if the ship of fools coiuld only quit fighting a hockeystick on request on Thinktank and along with Thinktanks notes and prescriptions / doggggggg- mae holy scriptures the Perinde ac cadaver- way, even fools on a ship can be rescued and re- educated rather on basic science and proper orientation in the universe.
specially at Kforestcat:
Yes, really, AMEN AMEN!
They managed to rescue the Giktgass CO over the Iron blast furnaces and drive the recently invented “Otto-motor” by it, to drive the blast, and to produce electricity for the electric arc lamps at the factories. Thus a very valuable resource, not to be wasted.
Having no “sea coal” in Norway and cokes not for sale anymore, I have had to fall back on real traditions and use….. “forest” as I preferre to call it for welding iron and fuse and cast aluminium and even bronse and gold.
A sack of charcoal ready and a vacuum clener for blast makes wonders, and sawed wood into “Knott” meaning nuts and proper blast under it, beats a large and very expensive Propane- flame whenever you need it, which is not often enough to buy that gas device. “Skog” = Forest, does it! a sack of charcoal, ae and saw, wreckboards, an electric ventilator but also a huge enough blast belly handdriven forfinest work, is really very practical. Fireproof stones and clays are found in nature. And for tecnical learning, go and see in the historical museum in the iron age, the golden age and the stone age departments. That is how!
The finest and cleanest coals are standing on root on the upper moors and heathers.
But I have often wondered why wood and “forest” is not fractioned and utilized better, because that exotic material is really very clean and in many respects better than “seacoal” fossile coal.
They have driven both glasswork and ironwork and silverwork and copperwork and tile and brickwork on it. But in recent time, only celliulose. fibers are used and half of the logs are going right into the river. Quite barbaric is n`t it?
Burt you know,…. the Norwegians….they are no more what they were and what they ought to be.
Then you have the synthese gases that you write of.
Compulsary things ought to be done such as allways have rooms and appartments for sale in the 2nd,3rd and 4th.. floor of a glasswork, because that is traditional. I heard that a man did actually live atop of the brickwork oven all through the winter, when that tilework really was in order and profitable.
Casting iron and aluminium should be shown to Finnmark where they have to heat in any case, and only work in the winter. Heating processes should be seasonal work on right locations. Thus my wife tells me to cast that aluminium and bronse in our stove only in the winter.
But I must blast a bit outdoor also if the things are too large, and then the heat goes right up to the crows. I am more concerned really that I cannot save and secure the gas, because that is what proper industry does. We save the ashes and bring it back on the apple- trees.
And this from my side is only in order to study it a bit in order to understand it better. It does pay off even on smallest scale. Understanding seems to be both valuable and profitable and maybe even sustainable, thus a quite valuable ware and resource.
Heating up the wood is also draining a fossile resource if we do not care for the green values , the photosynthetis and that it actually grows up faster than we take it and heat with it and eat it.
And that has actually been a severe problem in central Europe and in England, wherefore they began rather to dig and heat up the fossile “sea coal”. It did save the rests at least, of the european forests and moors and swamps..
Equally, Greenpeace did not save the whales. The whales were saved by “Sir” Francis Drake who found oil in Pennsylvania.
We exel in hydroelectric power here.
What is also quite important is to place it raher where you also have an icy creek to cool the process also. They loose…. when it is too hot in the summer for the cooling of nuclear, coal, gas and oil based electricity. Thus Snow and ice is also a quite valuable resource. Then you need no electric cooling device for the condenser.
I thought of demonstrating a responsible machine, using a re- cycled low compression ottomotor and run it on cheapest possible kerosene and adjust it to run as clean as possible. But then having a long restaurant buffet along with the exhaust- tube, with Samovar and hotdogs and even warm “toddy” or tea and coffee and hot boillion , for sale at the free market. plus selling electrical light for people also. And heat the room for frozen people with the cooler fan. To demonstrate how to use the heat at all its temperatures. Then the hardly more than 15% efficiency of that machine can be fully defended,. because people fuel and burn and heat in any case.
Although there is obviously no net energy gain, and greenhouse b.s. aside, could this process be used to ‘store’ solar energy and other intermittent sources to make these sources more useful?
oh heck, I can do that with a Hibachi grill.
Hmm, a more environmentally-friendly reaction would be: 6CO2 + 6H2O -> C6H12O6 + 6O2 which can use an energy source as simple as sunlight. The resulting carbohydrate can also be used for a variety of applications, including plant food.
Oh wait, that’s already been done.
2(C + 02) gives energy + 2 CO2, then 2 CO2 + cat + energy gives 2 CO, then 2CO + O2 gives 2CO2 + energy it’s called perpetual motion
rgbatduke,
Yes, there is a net energy loss. However electricity can not be stored efficiently where liquid fuels can be. CO2 + H20 + energy + catalysts may be a more efficient way to have “electric” cars than trying to drive cars from batteries charged directly from grid power.
“Ideally, Jiao said, one would like to convert carbon dioxide produced in power plants, refineries and petrochemical plants to fuels or other chemicals through renewable energy use.”. So it’s seen as a possible way of storing unreliables’ energy, not as a perpetual motion machine.
Reducing greenhouse carbon dioxide emissions from fossil fuel use is considered critical for human society.
If this was the primary motivation, then they may as well forget it.
tony nordberg and Graham:
You each ask if the suggested process could be used for energy storage from intermittent energy supplies such as wind and solar. The short answer is, Yes. However, I have doubt concerning practicability and feasibility.
My doubt is because in the 1980s the Technion Institute in Haifa developed a similar system for forming CO as an energy storage for solar boilers. Nobody has adopted it.
As I understand the above article, what is reported is a new catalyst and not a new process. So we are discussing the use of a cheaper catalyst to do what the Technion Institute developed decades ago.
A safe efficient storage system would reduce the need for power stations by about a third because it would reduce the need for power stations to provide power when electricity demand is above the average level. The economic and financial benefits of this are immense.
If the Technion Institute’s method worked then it would have been adopted.
Richard
Sounds to be right on up there with carbon sequestration.
Though if there are industrial uses (that are price competitive) for the CO so obtained, than all for the better. But I don’t expect it will work as a “solution” to the “problem” of CO₂ emissions.
It looks like other have been on the case too. Will we have to worry about peak oil? Only time will tell but this is another example of why I keep telling Warmists to stop spreading doom and gloom about future energy – human innovation. These experiments and such like are going on day in day out behind the scenes.
Of course, we can already produce hydrogen electrolytically and the feedstock is even more abundant than CO2. Hard to imagine that CO2 would be a better route to store electricity, but in order to effectively use solar or wind on a large scale it will be necessary to figure out a way to store the energy chemically, so by all means do the research.
This has potential for using electricity during off peak demand and recovering CO2 from coal and natural gas fired power plants. In this age, I find the idea quite sane.
TRG says: @ January 31, 2014 at 12:36 pm
Of course, we can already produce hydrogen electrolytically
>>>>>>>>>>>>>>>>>
Hydrogen explodes CO does not. It just kills you quietly. :>)
Gail Combs says:
January 31, 2014 at 11:53 am
With nuclear as the power source, “The resulting carbon monoxide, he continued, can be used as an industry feedstock for producing synthetic fuels”
So much for Peak Oil. So with Thorium reactors and this chemistry, problem solved. :>)
Someone ring up Obama and then we can all go home.
Gail,
Someone wring up Obama (sarchasm intended) and tell him We have +200 years supply of coal within the contiguous United States that yields prodigious amounts of thermal energy with little more than a single match needed to start the reaction. The reaction also produces CO2 gas, the direct and essential food source for all flora on this CO2-starved Planet Earth. In exquisite symbiosis, the plant based conversion of CO2 to plant matter plus O2 then directly and indirectly feeds all fauna on Spaceship Gaia while providing the oxygen critical for animal respiration and life. Completing the cycle of earthly life, every exhaled breath from planetary fauna yields more CO2 for the plants, while the animals waste products and decomposing bodies return essential nutrients to the flora. Coal Combustion: It’s a beautiful, ‘green’ part of the Cycle of Life!
Then he can go back to the golf course for the next 3 years, where he his ignorance and ideology can little hurt the planet and its denizens anew.
Mac
PS: And somebody tell him to replace his damn divots…..
R. Shearer says: @ January 31, 2014 at 12:36 pm
….. In this age, I find the idea quite sane.
>>>>>>>>>>>>>>>
If you want sane go thorium nuclear. That is what China is doing.
http://www.world-nuclear.org/info/Current-and-Future-Generation/Thorium/
I agree with those suggesting it is a potential way to store excess energy. That will, of course, lead to zero ‘carbon’ sequestration. That will not please the CAGW faithful.
Seems a variation on this Israeli process which uses waste heat –
Claimed new CO2 disassociation process presumably exothermic
The announcement on 14 Jan is the one –
http://www.asx.com.au/asx/research/companyInfo.do?by=asxCode&asxCode=GER
Market capitalization for GER AU$13mill,
Boy, then we could use the CO to make more the useful H2, using the water gas shift reaction … plus more CO2 of course.
Gail Combs says:
January 31, 2014 at 11:53 am
“Someone ring up Obama and then we can all go home.”
You hadn’t missed an “st” off that, had you? ;>)
There, fixed.
Heat of combustion for carbon monoxide is 10.112 MJ/kg while it is 32.808 MJ/kg for carbon. However, for 1 kg carbon content, that is, for 2.333 kg carbon monoxide it is 23.595 MJ. Which means, if the 92% efficiency of the new catalyst is taken into account, one needs some 78% of the energy content in carbon (coal) to convert flue gas electrochemically back to raw material for useful chemicals. Efficiency of power plants is lower than that, therefore one would use up all the coal and still need electricity from the outside. Power output of such a plant is strictly negative.
On the other hand sane people have figured out a long time ago how to burn coal on low oxygen directly to carbon monoxide, with positive energy output, some of which can be used to generate additional electricity.
That’s how smart these guys are.
A catalyst to convert CO2 would be great. I mean zero CO2 based emmission taxes on my Jeep
The end of Carbon taxes on everything… oh just a mo… that would mean billions less cash in UK & EU coffers ….
Disputin says: @ January 31, 2014 at 1:33 pm ….
ROTFLMAO Unfortunately they would find another puppet.
I wonder which one they will pick for us next?
The idea of a bunch of loose cannons geo-engineering the world in some new image scares me silly.
We are still working on finding out how this world works.
Swapping a plant fertilizing gas for a deadly one sounds like a poor deal to me. The fact that it is costly, difficult and pointless suggests that it should be ignored.
They made Cyclon-B with about the same efficiency and they weren’t seeking profit motive for that either. Wankers!
Oh the stupid…
Looks like everyone got there before me. CO2->CO is just a silly thing to do, and burns more fuel than it creates. How much more? Well look up Faraday’s constant and then factor in the various (in)efficiencies.
Even more stupid than carbon capture & storage – but useful for a “now scientists have discovered…” fund seeking press release.
I seem to recall it was the electro-chemists who brought us “cold fusion” (not).
I await news reports that everyone in the building is dead due to carbon monoxide poisoning. “Someone left the conversion machinery on overnight and gassed everyone.”
All this money being spent to find expensive ways to do something that plants do anyway. There is a photo of a trial plant taking power plant stack gas into glass tanks to grow green algae for STOCK FODDER in Queensland. The background to the photo is extensive lush green grass pastures. I suppose this nonsense won’t stop until nations have to legislate to outlaw these processes to preserve enough CO2 for the environment!
Pat Frank and a few other have it exactly right. If CO2 is not going to cause CAGW then using it for anything related to energy is a total waste of money. … use it for plant food where sunlight converts it back into an energy source absolutely free of charge. CO2 is nothing but a “dead battery” when it come to energy. It takes more energy to convert it back into an energy supplying form than you will ever get out when you reburn it. If you improve the process you might lose less money than you would with the unimproved process but you will ALWAYS lose.
Also, since the rate of photosynthesis increases with CO2 concentration, that means the increased photosynthesis rate is helping to cool the planet as a higher fraction of sunlight (energy) reaching the earths surface is being stored in C-H bonds rather ending up as waste heat. So what is not to like about increased CO2 if no CAGW?
As it has been said (by an 8 year old), “TheyPAY adults for this???”
The usefulness of such research depends on being able to scale up the process by a large factor while reducing the price. I do not see this process making competitively priced fuel any time soon, but I am glad that the research is progressing.
Oh my god! We take a harmless, odorless, trace gas which is necessary for life itself; call it an evil pollutant so that we can change it into a harmful, odorless, trace gas that is deadly to life itself.
Another example of humanity’s two steps forward, one step back approach to life.
I think we’re making a mistake reacting to the fact that carbon monoxide is poisonous. Many chemicals that are of great utility to humans are poisonous if ingested, but we have other uses for them.
In this case, the issues are not “is the result poisonous?” but “is it practical in the environment of a stack scrubber or similar situation?”
It’s a catalyst, apparently, with a small input voltage needed to pull off the trick. In other words, the normal energy calculations of combustion and conversion don’t apply. There are similar mechanisms now, using silver arranged in a crystalline structure. The arrangement in the paper has a tremendously larger surface area, and this seems to be the major trick. The shape of that surface area makes the rate of conversion high, it seems.
This all sounds good. But how delicate is it? And how fast? We don’t know — but the hint is that “we’re not there yet” since they hope their work “paves the way” for further advances. This is a reasonable if optimistic statement.
We should be leery of simply saying “carbon monoxide = bad!” It makes us sound rather like the catastrophists.
===|==============/ Keith DeHavelle
A few hundred square miles of green houses around the coal plants, using the waste heat and the CO2 would benefit every one.
Power plants in cool or cold climates could be a local major source of temperate and tropical fruits and vegetables. The heat and CO2 would be virtually free. Win Win. Greenies where are you.
Harmless trace gas (necessary for photosynthesis) -> deadly poison
Great deal, isn’t it?
Why bother with this reaction?
Frankly I’m highly skeptical of claims regarding electro-catalyst processes simply because: 1) you have to use very expensive electricity to drive the reactions, 2) you have to use more man-made energy than proceeding the other way; 3) these types of reactions typically require operation at or near atmospheric pressure.
Typically low pressure processes are too large to be commercially competitive. It’s a matter of economies-of-scale. Pressurized processes typically require less steel per unit of product produced; because, the process equipment has smaller pipe/tank diameters than lower pressure system. This is a lesson the non-engineering academic community constantly fails to grasp.
(To be fair scientist in question… please keep in mind I did not pay the fee required to read the paper… so I was not able see if the reactions were being conducted at low or high pressure.)
Moreover, as a chemical engineer, I am highly skeptical of claims of economic viability when only carbon monoxide (CO) is being produced by a proposed process. While CO is a useful building block, it’s is only useful to the extent that excess hydrogen (H2) is available for conversion to higher hydrocarbons.
Simply put… it’s the cost of producing hydrogen, not CO, that makes hydrocarbon production expensive.
So, the proposed process makes no sense to me. Why make expensive CO (only) when you can inexpensively make both CO and H2 at the same time?
At present we ready and economically produce both CO and H2 via either the steam-reforming or the partial oxidization processes using natural gas as a feedstock.
The primary reactions are:
1) Steam-methane reforming
CH4 +H2O => CO + 3 H2 (mildly endothermic – energy consuming)
2) Partial Oxidation (synthesis gas process)
CH4 +O2 => 2 CO + 4 H2 (exothermic – energy producing)
Generally speaking steam-reforming is the less expensive route of these because 1) water is a cheap reactant compared to the pure oxygen needed for partial oxidation, 2) the nickel based reforming catalyst is inexpensive and fairly robust, 3) the energy required for reforming can be supplied with excessive combustion; 4) steam-reforming processes are generally more energy efficient than partial oxidation processes, and 5) the reforming reaction occurs at moderate pressure (about 40 atmospheres) which allows the construction of plants with exceptionally good economics of scale.
Technically it is possible design lower pressure partial oxidation process with lower capital investments than steam-reformers. But, this isn’t necessarily true when you’re trying to make higher value products downstream; because, the downstream reactions typically require higher pressures.
By illustration… the next level of useful building block chemicals are methanol and ammonia. Both require the availability of excess hydrogen to be produced economically.
For example, to make methanol with the reforming process requires the use of a common copper, zinc, and alumina catalyst at operating at 50-100 atms, 250 C, and a selectivity of greater than 99.8% via the primary reaction:
CO + 2 H2 => CH3OH
The excess H2 molecule produce by the reformer (see reforming reaction above) is converted to methanol via reaction of excess CO2 via the reaction:
CO2 + 3 H2 => CH3OH + H20
The excess water produced above in the reaction above is consumed in a water-shift reactor via the reaction:
CO + 2 H20 => CO2 + H2 (exothermic)
For ammonia (NH3) production the required steps are similar:
1) Steam-methane reforming
CH4 +H2O => CO + 3 H2
2) Water shift reaction (to optimize hydrogen production)
CO + 2 H2O => CO2 + H2
3) Carbon dioxide removal (simple and cheap physical absorption with an amine solution)
4) Methanation to remove residual CO and CO2 via the reactions:
CO + 3 H2 => CH4 + H20
CO2 + 4 H2 => CH4 + 2 H20
5) Ammonia production via the reaction:
3 H2 + N2 => 2 NH3
Bottom line…. You can see the inherit advantages of these processes ability to produce both CO and H2.
So… again why bother converting CO2 to CO?
Now we have chemistry grads who didn’t take the thermodynamics option. Also, sheesh, what in hell would we do with a few hundred gigatonnes of “products” made from the 30Gt of Anthropo CO2 annually. Stupid, I know, but I’m going to investigate silver futures and … er coal investments. Scientists used to be more careful about announcing stupid things.
Their next project is to turn gold into lead.
Nah.
Gold from silver leads in the futures trading because of carbon.
But really,
Lead bearing on papers pouring into journals turning into promotions, touring, silver awards and gold coins. (As opposed to lead pouring into journal bearings around shafts turning silver commuting carbon unto copper … And if you understand any or every part of THAT particular pun you can only be a power plant engineer …) 8<)
However CO is much more reactive than Co2 For example we could turn CO and powdered Iron into Fe(CO)5 to sequester it. This would have the pleasant side effect of making both my Aurora and BHP shares go up!
Well… I use a charcoal grill in the summer. Plenty of CO coming off that baby. That is why they tell you to never use charcoal to heat your house: CO has a nasty habit of killing you. My boss did that in his car in his garage 30 years ago. And we buy CO detectors [for] our houses in case the furnace exhaust gas has a leak while heating the house with forced air.
Me, I think we have enough problems with CO, and not enough issues with CO2. And with CO2 being .04% of the atmosphere, and hoping global warming IS actually happening, so that maybe one day I can visit my Mom in Chicago when it is not 14 below zero. I think global warming is a good thing up to a few degrees or so. We will adapt, just like those of us who moved to the Southwest to avoid winters like my Mom had in Chicago (just like when I grew up in 1967 when it was also 14 below and I got to get our of school for a couple days). We adapted in Vegas with air conditoners during the warm months, otherwise it is the best climate I have lived in…even better than San Diego and the months of ocean gloom and clouds people forget about much of the year: clammy.
So bag the CO, we have enough of it. CO2 still gets my vote.
Keith, “It’s a catalyst, apparently, with a small input voltage needed to pull off the trick. In other words, the normal energy calculations of combustion and conversion don’t apply.”
That’s not how catalysts work. They only make a chemical reaction faster. They don’t change the reaction free energy (deltaG).
Turning CO2 into CO will always be an energy loser. Doing it electrolytically, with any kind of catalyst, is not a good way of storing off-peak energy. It’s not a good way of producing a feedstock gas. The CO won’t be useful for anything, including any chemical synthesis that might require CO. CO can be made other ways and much more cheaply – by the water-gas reaction, for example, that someone has already mentioned.
It’s an excellent piece of chemistry. It’s interesting, and the work could well point to better ways of making catalysts. The chemists deserve our congratulations.
But as a way toward “sustainability” (whatever that is), or carbon sequestration, or energy storage, or anything else economically useful, it’s a non-starter.
I suspect Heir Doctor Professor Feng Jiao missed the lecture on the Second Law of Thermodynamics.
richardscourtney says:
January 31, 2014 at 11:57 am
“It would be much better to obtain CO from coal using a water gas shift.”
Shift reactors go in the other direction. CO + H2O -> CO2 + H2. They are commonly used in reformers for cracking NG to produce H2.
Uh, no.
The laws of thermodynamics still apply. CO2 to CO still requires more energy than CO to CO2 provides. A catalyst cannot change that.
No, it’s just a silly statement. If you want CO from hydrocarbons, then make it from hydrocarbons directly. Turning the hydrocarbons into CO2 first just wastes energy.
On the other hand, if you happen to have a bunch of extra energy just laying around, such that you can afford to waste it reforming CO from the CO2 that you made by burning hydrocarbons for energy, then why not just use that energy laying around directly instead of burning the hydrocarbons in the first place?
A team of researchers at the University of Delaware has developed a highly selective catalyst capable of electrochemically converting carbon dioxide — a greenhouse gas — to lethal carbon monoxide with 92 percent efficiency. The carbon monoxide then can be used to exterminate humanity and kill off all plants.
The green cult will love this one.
I talked to the trees in my front yard about this. They, as well as the flowers, shrubs and grass in the area, are quite against this sort of exploitation of their food supply and have asked me to file a class action lawsuit against these fiends for plotting the mass murder of plant life. Or something like that. It is so cold outside that it is difficult to understand the trees, shrubs are never clever, the flowers don’t talk so much as blink their bulbs at this time of year and grasses tends to babble about everything at once. But they are again’ it and will sue.
Nobody “commonly” uses such catalysts to chemically synthesize anything useful from carbon dioxide. Nor are they about to. If you want to make carbon monoxide, then you can do it cheaply by the incomplete combustion of carbon, methane, or a gazillion other petroleum products.
Reducing carbon dioxide, which is what they are doing, is like selling dollar-bills for 50 cents. Leave it to the trees.
The current economic utility of such catalysts is close to zero, and will remain zero for the foreseeable future, and probably far beyond.
“The resulting carbon monoxide, he continued, can be used as an industry feedstock for producing synthetic fuels, while reducing industrial carbon dioxide emissions by as much as 40 percent.”
Using the CO to make other useful chemicals, sure, but using it to make fuels is stupid. It will take more energy to make the fuel than they will get back when they burn it. It’s impossible to end up ahead. Simple thermodynamics.
Seems to me this might be exciting news for those planning Mar’s missions – relying on Martian manufactured fuel, for the return trip. GK
Sorry. We already have the best living through CO2 conversion chemistry. The chemical process is called photosynthesis. The process converts CO2 into delicious food for human consumption and oxygen for humans to breathe. It doesn’t get any better than that.
This is ridiculous. Don’t you see the real agenda? Creating a process that can be patented and licensed for profit. If you really want to remediate CO2 , plant trees, cut them down when mature and make them into pellets to fire home furnaces and electric plants. Repeat. Oops sorry there’s no carbon credit patent royalties in that model.
rgbatduke says:
January 31, 2014 at 11:34 am
_______________________________________________________________________
Some of us organic chemists stayed awake in PChem.
All the catalyst does is decrease the activation energy and doesn’t affect the overall “deltaH”. If you look at cooling the stack gas, dewatering it and putting it through some separation process (membranes or zeolite absorption) with very likely compression to something north of 250 psig, the overall energy balance looks even worse.
The next great idea for carbon sequestration?
Think of it this way. What if it does work? And if the cost is not so much.
I don’t think we need it, I think we’d be just fine without it.
But what if it does work? Then things could go back to the way they never were. I’m so tired of this fight. I want it to stop. I want us to stop tearing each other apart.
Let me know when they perfect the ideal application for this type technology. You know, when they harness the limitless absolutely-free energy from photovoltaic solar panels, and crack the CO2 all the way down to O2, ready to be bottled for numerous purposes, and the carbon is electro-deposited onto microscopic seed crystals until it forms a usable compact product suitable for safe long-term carbon storage, such as two caret diamonds. In time they could stockpile perhaps millions of tons of them.
Because the way the better-than-thou eco-elites are killing off anything resembling a fossil fuel to save the world from global warming as the natural global cooling phase takes over, it might be worth a chuckle in the dismal times ahead to toss another shovelful of diamonds on the fire to stay warm.
It’s just that I have been in this fight for so long. I’m so tired.
evanmjones,
Relax, we can tag-team. ☺
evanmjones said January 31, 2014 at 9:06 pm:
Mother Nature has come to your defense as the natural cool phase has taken hold. As “The Pause” grows longer and tilts negative, their rhetoric shall be hard-pressed to find willing ears.
Take some time off, relax, recharge. Just don’t forget to come back to the battle when the warm phase returns and they start up again, in about, oh, twenty years.
To the various know-nothings that think producing CO is a bad idea because it is poisonous: There are many industrial gases that are produced in large quantities and that are highly toxic. One common one is hydrogen sulfide, which happens to have an odor we are all familiar with. CO is also already produced industrially. People used to cook and heat their homes with coal gas which contained a high percentage of CO.
Riiiight? Conversion of CO2 which is necessary to life to CO which is inimical to it? That sounds like a great idea! Aren’t there better ways of producing industrial CO?
We are well aware of the other industrial poisons cited by TRG above. Just because burning coal produces CO doesn’t make that CO safe. We use a CO detector at home as we have a solid fuel stove.
Kforestcat \at 4:21 pm
says it very well.
This (?) 2 CO2 –> 2 CO + O2 reaction makes little sense from a process point of view.
Take C (coal) to CO in the first step of combustion is nearly a wash if not endothermic.
It is the conversion of CO to CO2 that is the primary exothermic reaction to generate useful energy.
So where are you going to get a concentrated CO2 stream to run this highly endothermic catalytic reaction? From a powerplant that uses almost all the power to reverse the process?
The energy budget of this process needs further explaining.
About the only thing this catalytic process is good for is generating government grants.
Neither of these compounds play well with their neighbors. Build such plants any place you want but no closer than a 2 hour drive away from my back yard. Just one of the many problems:
http://metallurgyfordummies.com/hydrogen-embrittlement/
~~~~
And note, TRG just above, says “People used to . . .” Good riddance.
The energy balance of generating and re-burning the CO isn’t terribly relevant. The comparison should be to other ways of creating feedstock and chemicals, period. It may be fine for that purpose. Impact on CO2 emissions and levels is beyond negligible, of course.
Daryl M:
Sorry, but you are very mistaken in your post at January 31, 2014 at 6:28 pm which says
No. I don’t know why you think there was a demand for hydrogen in 1828.
My post rightly said
And part of that wicki explanation says
Richard
From Carbomontanus on January 31, 2014 at 11:19 pm:
Bah! You are a vile burner of charcoal and wood, a lowly creature indeed, who undeservedly besmirches the great reputation of modern forge propane burners!
At the ABANA website (Artist-Blacksmith’s Association of North America Inc.), they host Ron Reil’s old site. A true innovator of modern naturally-aspirated venturi propane burners, he had a decorative metalworking business until recent health problems. Much like yourself, he did blacksmith work, including forge welding, and the casting of iron to aluminum. Might still be doing it too as a hobby, however the old site is now archived.
From his Forge page (yes, the site is messy), you can read about his blacksmithing history, equipment, and his forges, coal and propane, that he has built himself. On the Forge and Burner Design pages you’ll find many designs for efficient and powerful propane burners, that you could cheaply make for yourself from common plumbing fittings. I made an “EZ-Burner” variant myself some years back, it was easy.
There are actually a great many US blacksmiths and other metalworkers who make their own forges, and also potters and glassblowers who make their own kilns. Propane can be very cheap to run.
You said:
Except in these modern times, it’s just not worth it to use such primitive natural materials. You have to invest a lot of heat and time to warm up those dense stones and clays, or even “traditional” hard firebricks, and the investment is lost when you’re done working and the forge is left to cool.
Use the modern lightweight soft firebricks, or the insulating blanket refractory materials like Kaowool. Fire off a propane burner or two, get to welding heat in a minute, have the forge cool right away when shut down and with no burning embers or ashes to worry about.
If you think propane is too expensive for your metalwork, you are obviously using the wrong equipment. Check out the many plans, build your own forge.
CO2 is good for plants and therefore the environment. CO is a deadly poison.
Sounds like a good plan to me if you let those enviro-nuts breath it.
I believe Carbon monoxide is key to the Fischer-Tropsch (FT) process.
http://enerdynamics.files.wordpress.com/2012/07/516px-gtl_process.gif
Forget Carbon capture and storage, think…..
Carbon capture and diesel production.
If we were at the point where we were out of fossil fuels, but we had an robust infrastructure of, say, nuclear power, this would be a good method of producing high energy-density hydrocarbon fuels for moving vehicles, or for storing energy for usage in peak demand periods. But it is by definition not an energy source — it will always be a net energy sink. Oxidizing carbon into CO2 is like letting a cart roll down a hill. Reducing it back into CO is equivalent to pushing the cart back up the hill. By the laws of thermodynamics, it always takes more energy to get it back up the hill than was released when it rolled down in the first place. If they are claiming 92% efficiency, then the energy loss in their process is 8%, so if you expend 100 joules making CO out of CO2, you’ll be able to get 92 joules out of burning the subsequent CO products. The other 8 joules went into heat somewhere — most of it probably from current in the electrical wires. Always a losing proposition. Sorry.
You canna change the laws of physics or thermodynamics. It would have a niche for sure but as a solution for carbon dioxide emissions? Forget it!
John F. Hultquist says:
January 31, 2014 at 10:54 pm
Neither of these compounds play well with their neighbors. Build such plants any place you want but no closer than a 2 hour drive away from my back yard. Just one of the many problems:
http://metallurgyfordummies.com/hydrogen-embrittlement/
===================================================
Thank you very much for the link.
This is the dumbest article you have ever posted. And a further argument for getting the government out of funding research at US universities; there is no science left just broad deep endless irremediable stupidity.
I think I figured out my investment problem.
I’d like to invest in a good idea but Washington and the powers-that-be invest taxpayer money and promote really wasteful, useless and dumb ideas that get them lots of money and power.
I know as soon as I do the people will wake up and make them stop this nonsense.
But, if I invest in a good idea they’ll regulate it until its head is underwater and it dies.
e.g.
Wind mills bad idea – good investment.
Nuclear power good idea – bad investment.
General Motors good idea – bad investment
Hedge fund bad idea – good investment
Oh the ironing.
cn
Richard Courtney,
The water gas reaction using coke as the carbon source was pert of the town gas supply in the UK before the advent of natural gas. One piece of trivia is that the process is the source of the expression of “Being asleep at the switch”. An operator would manually switch the reactors from steam blow to air blow approximately every 20 minutes, a somewhat boring job. Being asleep at the switch would result in the coke mass dropping too low in temperature for the reaction to occur and hence mostly steam being injected into the product gas stream.
Mike Singleton:
re your post at February 1, 2014 at 8:24 am.
Thankyou for that interesting “piece of trivia”. I did not know that and will use it when appropriate.
Richard
Tough crowd.
I wasn’t involved in this study, but I did publish a reasonably high-profile paper on the catalytic reduction of CO2 to CO, some nine years ago, and so I can’t help feeling implicated when various commenters point out that CO is much more toxic than CO2, that the reaction requires a thermodynamic input, that these people are idiots, that this won’t cut down on overall CO2 emissions, and that this study demonstrates why the government shouldn’t fund research at universities.
At the risk of sounding defensive:
– I am not a green cultist. I believe the strongest feedback loops in the study of global warming are confirmation bias and the Texas sharpshooter’s fallacy, and my response to people who get dogmatic about CO2 as the principal driver of climate is, get back to me when you understand clouds. I do not dangle even the theoretical possibility of greenhouse gas remediation in “selling” my research.
– I am well aware that CO is toxic. In fact, a standard line in my talk about this portion of my research is, “So we’ve just turned a nontoxic, nonflammable gas into a toxic and flammable one, which looks like a really stupid thing to do.” But only at a glance is it stupid. Chemists, unlike plants, are really bad at making useful plants out of CO2. We are really good at using CO as our one-carbon building block. In other words, you don’t need to release that toxic gas; you can keep it in the vessel and use it to make some value-added product.
– OK, but the energy has to come from somewhere! Right, so I freely admit I have not, on balance, removed a single molecule of CO2 from the atmosphere. Which is beside the point: Say you think renewables will forever be a boondoggle, but someday we’ll generate all the energy we need from thorium fission, or better yet deuterium fusion. The lowest-tech way to integrate such a boon to mankind with the transportation infrastructure we have now is conversion to high-energy-density chemical fuels. (There’s a case to be made for batteries; my opinion is, we’ll need better batteries.) Look at all the efforts to use hydrogen as that currency. Liquid hydrogen boils at 20K and has a density one-fourteenth that of water. If you can turn CO2 to CO, you can, as pointed out above, make diesel out of that; and there will certainly be better CO2 to liquid fuel conversions down the road if the payoff becomes more obvious. But only if you can run such reactions efficiently, with little wasted energy, would it ever scale. Does this reaction scale? No. Is it a step toward being able to make and break bonds without wasting too much energy? Yes.
– When I get cynical about synthetic CO2 chemistry, I ask myself, what would be the ideal catalyst? Well, it would need to be air- and water-stable. It’d be good if it would take in CO2 at 400 ppm, rather than requiring concentration. It’ll need to take its energy input from light, make a product we need an awful lot of, and it’ll need to be something that scales beyond imagining. Yes, I’ve just described green plants (which I think is why a lot of old CO2 chemists turn to biomass conversion chemistry late in their careers), and yes, there’s a case to be made that even biofuels aren’t going to become viable very soon. Still, there’s something to be said for concentration effects, and again, if you have a nuke plant and want to produce vehicle fuel, turning CO2 to liquid fuels is arguably not an idiotic solution.
JPS:
I write to support the principle of what you say in your post at February 1, 2014 at 8:32 am.
And there is a much, much more important reason for the development of
CO2 –> CO
with great efficiency than production of chemical feedstock.
If it could be achieved then it would be immensely valuable now. I draw your attention to my post in this thread which is here.
The potential benefits of this would be so great that it merits as much research effort as thorium and fusion reactors combined.
And those who are concerned about hydrogen embritlement and the corrosive nature of hot, reducing gas need not be concerned. I solved that problem more than two decades ago as part of my work on the ABGC process.
Richard
Richard, thank you for this, and for your earlier, interesting posts. I’d read that comment but not fully registered it, I think. I’m interested to learn more about this Technion work.
I will add this to my too-long post: It’s hard to get people to pay for your research if you just say, We thought this was fascinating and challenging, so we decided to take a crack at it and here’s what we found. So a lot of papers on CO2 chemistry begin with ritual incantations about CO2 and climate change, and the indirect suggestion that this research might help Solve the Problem.
I don’t like it, and my hero in the field (a real pioneer in fundamental CO2 chemistry) cautioned me early on against ever implying that this chemistry might make a difference in atmospheric CO2 levels.
Get ready, folks are starting to realize that carbon dioxide is a resource to be used, and not a pollutant to be pumped far underground in geological storage! It is a wonderfully useful product, folks will soon be fighting for the rights to buy CO2 from smokestacks.
This New Zealand company converts carbon monoxide into various chemicals via biotechnology:
http://www.lanzatech.com/content/lanzatech-process
I think these schemes are exciting! The first airplanes, cars etc. weren’t especially energy-efficient or cost-effective, but once refinements were determined, they spawned vast new industries. Carbon dioxide could do the same.
Likely, neither are the authors of this study. But they chose to frame their work to fit the green cultist memeset and play to warmist ignorance, by saying absolutely asinine things such as:
And that is why they get the “hard crowd” treatment. They deserve it, for saying stupidly anti-scientific things in and about a putatively scientfic paper, in order to fellate Big Warming and thus keep access to journals and $$$ rolling their way.
This phenomenon is far from restricted to the tiny sub-field of CO2 chemistry, of course. It is pandemic across nearly all scientific disciplines, and is the mechanism by which (similarly anti-scientific) claims of “consensus” are manufactured. Any scientist who participates in this BS deserves to have their hide nailed to the wall.
Richardscourtney, JPS, and Others
Richard: understand your background is in Air Blown Gasification. Nothing personal, but I’m not a real fan of Air Blown Gasification. I’m strictly an the oxygen blown, slurry fed, entrained-flow gasification man. Particularly when it comes to chemical production. No hard feelings. Pros and cons to both technologies. Just an entirely different perspective on my part.
As background, I worked on the Tennessee Valley Authority’s (TVA) commercial scale ammonia from coal project in the mid-1980’s, while working as an engineer and later as a conceptual cost estimator with the TVA’s Fertilizer Research and Development Center. The unit used a Texaco gasifier. Also worked on later proposals to build a 1,000 ton/day ammonia, urea, and electrical power co-production facility using the turbines of a partially built nuclear plant and a series of 2000 ton/day Shell gasifiers. Al Gore killed the Shell project when he became VP, which was a real shame because we would have paid for the entire project within three years of construction. (The USSR collapsed creating a short window of highly profitable ammonia/urea pricing… the window has since passed).
Richard and JPS. Can’t say I agree with you regarding the value of CO for energy storage. For energy storage I’m on the side of air and hydro storage. The TVA Raccoon Mountain facility being a prime example of cost efficient hydro storage. As for air, I believe recent advances in air storage may outstrip even hydro options.
I just can’t see CO chemical storage as being terribly useful for energy storage. Long term, I suspect CO could not compete with fluid battery technologies and I would be more inclined to see scarce research money spent on fluid battery technology instead. (Liquid storage being considerably cheaper/safer than CO storage). Again no hard feelings, just a difference of opinion. If you can reference cost literature I would be happy to reconsider.
As general note to the community (I’m sure Richard & JPS know this), I notice many of you are under the impression that coal is primarily carbon (C). Technically this is not true. Chemically, coal best described as chain of C-H molecules… typically described as C24H12.
For oxygen-fired gasification (in a reducing atmosphere) the partial oxidation reaction is expressed as:
C24H12 + 12 O2 => 24 CO + 6 H2
If chemical production anticipated (or for power applications) the syn-gas is typically processed in dual CO shift reactors via the reaction:
24 CO + 24 H20 => 24 CO2 + 24 H2
Regards, Kforestcat
P.S. I notice that I incorrectly described the partial oxidation of methane in my Jan 31, 2014 at 4:21 post above. I described the reaction as:
CH4 + O2 => 2 CO + 4 H2
This is incorrect (I missed a CH4 molecule) the reaction is properly described as:
2 CH4 + O2 => 2 CO + 4 H2
Sorry, in my hast, I failed to balance the equations.
Kforestcat:
I write to disagree with your assertions in your post at February 1, 2014 at 10:52 pm concerning the usefulness of CO as an energy store.
A fuel is a large store of energy which can release the energy in a controlled manner and not at rapid rate. This is why petrol (US ‘gas’) is a good vehicle fuel, but hydrogen is not: petrol may burn but does not explode in a crash.
Perhaps another illustration may be more cogent for you in the light of your stated background. Burning a kilo of dynamite releases LESS energy than burning a kilo of coal, but nobody would choose to use dynamite as a fuel.
However, you say to me
Oh dear, no. No. No! NO!
Please do not store megajoules as compressed air. It would be a bomb waiting to go off!
This is a classic, “It’s a good idea in the lab,” notion like high-alumina cement but with more fatal consequences. I would not live within a hundred miles of such an energy store because I would not want parts of the nearby towns falling on me when they came back down.
Have you never pricked a balloon?
The benefits of electricity grid smoothing are so great that it would be done if it were viable. Hydro is really, really good wherever it can be used, and if there were sufficient sites for hydro to be a solution to electricity output smoothing then it would be done. Pumped storage is economic for peak demand supply, but is expensive and lacks appropriate sites for it.
You also say
In the days of ‘towns gas’ CO was used as an energy store. Scaling to modern storage would not be a problem of any kind.
The physical size of batteries would be a problem, and fluid batteries also pose severe safety risks. If you think nuclear power gets opposition then think how difficult it would be to get approval for a large liquid battery store. However, the small unit size of such batteries would reduce the novelty risk of their introduction and would enable distributed storage over large areas (although such distributed storage would increase operational and maintenance costs). Anyway, I am extremely doubtful that such large battery operation could be technically viable in the foreseeable future.
CO2 –> CO would be a viable energy store if the conversion had sufficient efficiency. All the safety issues were solved in the nineteenth century when CO was used as a fuel in ‘towns gas’. And the CO is capable of cofiring with other fuels when the energy needs to be recovered. If the efficient conversion could be perfected then it promises to be a method for the needed energy store: indeed, it is the the only viable method which has been evinced to date.
Such an energy store would reduce the need for power stations by about a third and would reduce the difficulties of grid operation.
I only mentioned ABGC because hydrogen embritlement was mentioned in the thread and I failed to resist the temptation to boast that I devised and perfected a solution to that problem. However, none of the advanced clean coal technologies for power generation (including ABGC or yours) is likely to be adopted because of the high capital cost imposed by novelty risk.
Thanks for your comments.
Richard
Richard,
I am curious about your solution for preventing H2 embritlement, can you explain more fully or provide a link. I am not a metallurgist but I am familiar with some methods to avoid H2 attack and embritlement in the refining business.
Also I am curious as to how you would store large quantities of CO comparable to the energy in a million barrels of oil.
Thanks for your reply .
@richard & catcracking
Maybe you ought to know from this side.
We have a boat.
Suddenly and unexpectedly the propellar axis with pin and large button began to “rot” and break. The propellar kept, but was lost after 3 such events. And I had to read about it and ask people.
Common Plumber brass for freshwater does “rot” in seawater. The surface keeps shiny, but inside, it is copper- powder. And fusing on it betrays Cu powder embedded in ZnO.
How can it be possible?
Well protons H+ has to enter and diffuse through that solid metal and oxidize Zn.
To prevent it, the old book from 1915 tells of “Naval brass” containing 2% tin. And what keeps for centuries in seawater is “gunmetal”, high quality mallable tin bronse.
That`s it, and I am not too experienced, but copper you see is also a bit tricky. Brittle copper comes when it is warmed to red hot for too long and allowed to cristallize in too large cristals. It happens for instance also in electric material if that has ran too hot for too long.
And then we have the exotic situation of protons travelling rather easily in the electric lead bond of platinum metals, especially Palladium. Thus also the rumors of possible “cold fusion” by Deuterium travelling the same way.
But Protons H+ travelling rather easily in some metals solid state, that is reality.
Catcracking:
Thanks for the interest you express in your post at February 2, 2014 at 9:11 am.
I don’t know if my method for avoiding H2 embritlement and avoiding corrosion by hot reducing gas would work in the refining industry. I was seeking a method to obtain metals capable of being expansion sections in pipework, sensor shields, etc. in ABGC gas (rich in CO) at ~980°C. We were conducting costly exposure tests on exotic and expensive materials (e.g. Hastelloy X) which were difficult to fabricate, machine and weld. I demonstrated that 310 stainless steel (noted for its high temperature creep resistance) could be electroplated with gold to form a corrosion resistant barrier. A copper bond coat is needed between the steel and the gold. I was concerned that mercury from the gas would destroy the protective layer by forming an amalgam. However, theoretical calculations indicated the Hg would evapourate faster than it could diffuse into the Au, and this proved to be the case. The protective layer is only a few microns thick and needs protection from erosion by dust in the gas stream, but this is simply achieved by a protective barrier of ceramic cloth.
This solution was much cheaper than the exotic materials being tested, and 310 ss does not have the fabrication problems of the exotics.
An unexpected finding was that hydrogen does not cross the electroplated barrier into the steel. I do not know why. I have reason to think it is the Cu bond coat (not the Au) which inhibits the H2 passage. I have a few ideas about why this happens but could not pursue them because the Coal Research Establishment where the work was conducted was closed as part of the closure of the UK coal industry.
An interesting point is the reluctance of engineers to testing of the protective Au-layer idea. I suspect the prejudice was because they had a subconscious idea of a gleaming gold-plated chemical engineering plants. However, the Au-coated 310 ss works, is much cheaper than the exotic materials, and the obvious fabrication problems of the exotics are avoided. The used amount of gold is very small and cannot be stolen.
You ask how to store “quantities of CO comparable to the energy in a million barrels of oil”. A barrel is about 1.7 MWh so you are asking for storage equivalent to enable a 2GW power station to operate for about an hour. I see no problem constructing sufficient gasometers for that. Indeed, about 3 times that would be needed for complete output smoothing from a single 2GW power station, and that need not be problematic for a new plant.
I hope that is what you wanted.
Richard
Carbomontanus:
Thanks for your post at February 2, 2014 at 9:54 am which you provided while I was typing my post at February 2, 2014 at 10:14 am. I did not ignore your post: I did not see it until I had posted mine.
Yes, as my post says, I was surprised by the apparent effect of a 3 – 5 micron electroplating bond coat of copper between steel and gold. There is work to be done here because I don’t understand how and why the copper layer inhibits passage of hydrogen at temperatures at ~980°C, but I know it does.
Richard
Carbomontanus,
You are correct, as a long time boat(s) owner in salt water, I am well aware that normal copper does not cut it in salt water. One must user Naval quality usually Bronze for strength. Many a boat has been sunk with using the wrong valves or other fittings for thru hulls and other piping for equipment such as sea water used for wet air conditioning systems. I have a concern when I purchase fittings today that the foreign made fittings might not be suitable although the packaging claims it is suitable for salt water.
Richard,
Thanks for your reply,
I’ll keep that in mind as another means to protect steel, it is interesting although I have already taken heat for silver plating Ring Type flange gaskets. I assume you are talking about low pressures whereas in the Refining and Chemical business we are mostly at higher pressures.
In most high temperature applications we try via refractory linings to keep the metal temperature below 650 F even in expansion joints.
Also I find your storage tanks interesting especially after reading that water seals are used at the telescoping joints, although I don’t have a grasp of the details. The leakage issue initially raised concerns in my mind as to storage issues. As a child I used to pass a telescoping gas tank often and always wondered how they seal from leakage.
I still have significant skepticism about the catalytic process described in this post particularly on a commercial scale since separation of Nitrogen from the CO2 would be expensive where air has been used for combustion.
BTW the Cat in my name (catcracking) is an abbreviation from Fluid bed Catalytic Cracking which is a key high temperature processing stage employed in most oil refineries where we use refractories, expansion joints and high Ni Cr steels.
Again, appreciate your reply
Actually pure copper is relatively resistant to corrosion in seawater. What you are talking about is brass, a copper alloy using zinc and copper – most copper tubing is close to pure copper but the fittings used to join the tubing are mostly brass. The process which you described as rotting is a type of corrosion known as dezincification, and results in a spongy looking mass of copper which has no strength and leaks like a sieve. Tin or antimony added to brass will reduce the corrosion and is classified as corrosion resistant brass. Gunmetal is bronze and is an alloy of copper and tin and is resistant to corrosion. Naval or Admiralty Brass, was developed by the Royal Navy specifically to resist the corrosive effects, and is composed of approximately 69% copper, 30% zinc, and 1% tin. I’ve actually found that nickel brass (70% copper, 24.5 zinc, and 5.5% nickel) is the most effective for use in seawater, but is usually more expensive.
Zinc is frequently used as a sacrificial anode on seawater systems to protect against corrosion of other metals – if you are using a marinized engine look for the anode plugs, if you are not using a marinized engine, get some anodes fitted or your engine will be toast within a year or less. Same goes for any systems in contact with seawater or using seawater as their coolant.
BTW don’t use aluminum in contact with seawater – it corrodes very quickly, and if you use it connected to any stainless fittings it will bond like its welded making it very difficult to remove.
Catcracking:
Thanks for your reply at February 2, 2014 at 1:29 pm.
I don’t know what you mean by “high pressures”. The process operates at ~2 atm.
The temperature is limited to ~980°C because higher temperature causes slagging in the fluidised bed and highest temperature is desired. The plant design does use mostly refractory linings for pipework, etc. but – as I said – expansion lengths and sensor covers are intended to operate at gas temperature.
Gasometers have their name because they telescope and their height is a direct indication of their contents. That is why they have numbers on their sides. The exposed numbers provide a direct indication of how much gas is in the gasometers. A really clever piece of Victorian technology.
I, too, have doubts about the reported catalyst and I said that above here. However, as I also said, if an efficient method for the conversion could be achieved then it would enable immense benefits.
Incidentally, I lived on an ocean-going power cruiser for nearly five years to do a project and I returned to land-living about a decade ago. Sacrificial anodes need replacement annually and are expensive.
Richard
Richard,
Except for vacuum pipestills, 2 atmospheres would be the starting point for most Refining processes and pressures can run up to thousands of psi for hydrotreating and desulfurization processes.
I did a lot of engineering for petroleum coke, fluid bed gasifiers as part of a FLEXICOKING Unit process which use air compressors and operated at circa 1800 F . A low BTU gas is produced that was burned in furnaces in the refinery. Slag can also an issue with these gasifiers when vanadium is present in the feed.
Hmm This seems to have vanished. I will try again.
Catcracking:
Thanks for the interesting conversation and information. I have filed your technical info. for future reference.
I hope I have answered your questions. I don’t think I can add much more. I may have already said more than I should.
So, unless you have further specific queries, I am signing off from this with sincere thanks.
Richard
Richardscourtney:
In response to your Feb 2, 2014 @ 12:48 comments I offer the following:
First please keep in mind that I make a very good living creating utility generation/chemical process strategies to meet emission goals, develop policy recommendations, financing research, plan capacity expansions, recommend plant closures, and formulate comment on proposed regulations. I’ve been doing this for over thirty years… so, I’m no novice. This not intended to be an appeal to authority. Nor am I trying to puff myself up… lord knows I don’t know everything. But it helps provides context for what I’m about to say. And I’m open to dissenting views.
With regard cost of air and hydro pumped storage. Your correct that both technologies are good for peak power; however, I think your underestimating value of these assets at minimum load. Specifically that both systems save as much money at the minimum daily load as they do a the daily peak (if not more). Specifically, that at minimum load these assets minimize the need to shut -down units thus avoid the maintenance and fuel cost of start-up that may be required 2-3 hours later in the daily cycle.
In my view, in today’s market, a typical regional utility (serving several million people) will benefit if it has roughly 1,000-1,500 Mw of dispatch-able storage capacity. However, to be economically viable, each dispatch-able unit needs to be capable of 200-400 Mw per unit to capture the economics-of-scale. Further, each unit must be able to dispatch within 15 minutes – both in terms of storing and discharging power. And, ideally, all of the storage units must be available to accept power from the utilities entire fleet of generating units and the storage units must be able to discharge power to the grid in a manner that allows transmition to all parts of the grid.
The short version is, to make energy storage economical, you need a good deal of “system” storage capacity with individual unit capacities large enough to readily dispatch in on short notice
With regard to Compressed Air Energy Storage (CAES). Your comments regarding safety appear to related to small-scale above ground air storage. I was referring to large-scale underground air storage in the 200-250 Mw range. Several commercial units have been constructed since the late 1970’s; so, this is a fairly mature technology. Safety wise I’m fairly confident there will not be any “towns falling down” on you :).
With regard to your comment that hydro pumped storage is “expensive” . All energy options are “expensive”. The appropriate metric is wither they make economic sense. Until recently pumped hydro was the least expensive option for utility scale energy storage followed by CAES. Recent developments suggest CAES may be the lease expensive option.
Regarding your statement that pumped storage “lacks appropriate sites”. The same could be said of CAES which requires the presence of suitable caverns. However, because a typical utilities storage needs are regional in nature (see above) you really don’t need that many sites. In this context there are a more suitable sites than one might think. If you’re in a prairie state build a CAES. In a mountain state build a pumped storage unit or modify an existing dam to suit that purpose. If your state does not have a suitable site, build in an adjacent state or contract with another utility that has a suitable site.
With regard to your comment “The physical size of [fluid] batteries would be a problem, and fluid batteries also pose severe safety risks. If you think nuclear power gets opposition then think how difficult it would be to get approval for large battery storage”.
Well… not to trying to be offensive but the fact is I’m quite familiar with the environmental impact statements and hazard assessments associated with planned fluid battery projects – in particular one that was to be located in Mississippi in the early 2000’s (It was a polysulfide bromide regenerative fuel cell process). The hazard levels simply weren’t that high and there was no public resistant to the project . Unit size was 12 Mw and covered a mere 2 acres. The project was never completed because the company that owned the technology ran into scale-up problems and went broke before it could solve the problem. Concept wise, I’m more an advocate of the vanadium redox process myself; but the vanadium research/development communities products are currently in the 0.5 Mw/Unit range. This is too low a capacity to garner my immediate interest. I’ll start to get excited when the 10 plus Mw/unit range is achieved.
Regarding your comment “In the days of ‘town gas’ was used as an energy store”. I’m not aware of any storage mechanism (use of tanks etc) associated with town gas. If you could point to a source I’d happy to look it over. In my view the magnitude of storage required to meet systems needs requires roughly the same type/capacity of underground storage currently contemplated for CAES or seasonal natural gas storage. Loads issue can last a long as three days, so many people underestimate the amount of energy storage capacity required to pay for storage systems. As a general rule of thumb you’re looking at building roughly 24-30 hours of energy storage capacity with an expectation of fully discharging the stored capacity in 20-24 hours – to ride out mult-day incidents and optimize the economic benefits. Above ground storage is possible; but too expensive at this level of storage and the hazard assessment for high volume above ground CO storage is going to be tough – much tougher than ammonia storage. So I’d have to have a pretty compelling argument to use the CO2 to CO process to over the other options.
I’ll make one final set of observations regarding CO from CO2 process viability for energy storage.
The CO2 to CO process produces a gas that is distinctly different from ‘town gas’. Town-gas was typically produced by adding steam to the input air; so, the gas usually contained a considerable amount hydrogen in addition to CO. The hydrogen gave the gas a higher caloric value and improved flame stability. This distinctly different from the pure CO gas produced by the CO2 to CO process.
Should one attempt to use a pure low-caloric CO gas source in today’s technology I can foresee practical process problems. To begin, to meet the 15 minute start-up limit described above, we would likely have to use a Combustion Turbines (CT) to produce the electrical generation needed.
Today’s Combustion Turbines (CTs) are designed to use natural gas. In particular, a modern CT is designed to minimize NOx and CO emissions while burning natural gas. When one substitutes natural gas with say a coal-based syn-gas one has to modify both the sny-gas and the CT. Essentially one typically optimizes the syn-gas’s original CO/H2 ratio to increase the gas heat content (add H2) to ensure complete combustion and minimize CO emissions at ppm levels. The increased H2 also increases the flame stability which helps prevent flame-out and back-flash issues. The down side of increasing the H2 content is that the flame temperature increases NOx production. To counter NOx production, excess dilution air is added to the CT which lowers the gas temperature, but at the expense of unit energy efficiency… as the compressor providing the dilution air has to handle the increased air volume.
So, you’re likely to run into some problems when you try to feed a pure CO feedstock into these CTs. First off, I strongly suspect you’re going to hit serious flame stability issues – which can lead to safety issues… risk of flame-out and flash-back. Plus the flame stability issues could damage the CT due to intermittent mechanical shock. So, selling this concept to utility executives is going to be a “hard sell”. And good luck trying to get CT manufactures to modify their designs for a CO-only feed. We been trying to get a syn-gas optimized CT for many years.
Next, the CT’s combustion efficiency is likely to go down – way down – resulting in much higher CO emissions. So, at first blush, meeting the unit’s CO emission limit looks highly problematic.
Now one might try to argue that we could adjust the CO/H2 ratio using upstream CO shift reactors. But, the reality is we need steam to drive the reaction and CO Shift reactors operate a high temperature. So is unlikely that we’d be able to get the these systems operating in required 15 minute time-frame.
Likewise we can’t raise the steam in a steam system, simply because we can’t steam operational in the required time-frame.
At present, my problem with CO2 to CO concepts is that they don’t meet my real world operational needs – it looks like a process in search problem. If someone can point me to a CO2 to CO process layout that will actual meet a utilities needs I’d happy to be look at it. But, as it stands I’m not seeing the “carrot”.
Regards, Kforestcat
Kforestcat:
Thankyou for your post at February 2, 2014 at 8:57 pm.
You provide much useful information. Thankyou.
As my earlier posts in this thread demonstrate, I strongly agree with you that – assuming safety issues are resolved – the only thing which matters is economics. And I note you say
Well… not to trying to be offensive but the fact is that your comment I quote supports what I said and you have answered; i.e. I wrote
Your report says the example you cite did prove the battery project to be not viable because technical problems of scale-up caused the company to go broke.
I am not convinced by your claims that MWh stored as compressed air does not pose a severe disaster risk.
We seem to broadly agree about hydro and about pumped storage.
I am surprised that you ask
Every town that had a ‘gas works’ used gasometers to store gas (i.e. an energy store). Here is a picture which shows what they look like.
And I am fully aware of the differences between ‘towns gas’ and natural gas (i.e. methane or propane) and I am surprised that my comments in this thread have not – at least – hinted that.
We are not discussing ‘towns gas’ in this thread. We are discussing CO2–>CO with possible controlled addition of H2. I see no reasons for such a gas to have problems of flame stability.
Anyway, we are discussing potential tech. and there is no flame in fluidised bed combustors. Some are multi-fuel: we burned wet sewage as fuel in a PFBC.
You say
The problem exists of need for large scale energy storage for electricity grid smoothing.
CO2–>CO is a potential solution to it.
Unless and until efficient CO2–>CO exists there is no point in anybody designing a “process layout that will actual meet a utilities needs”.
Research to obtain efficient CO2–>CO is the subject under discussion in this thread.
Richard
@ Richard & Kforestcat al
Here is the sad side of it.
In Ernst G.Riesenfeldts Lehrbuch der anorganischen Chemie from 1946 4rth edition at Nobelinstituttet Stockholm I find notation of the Carbonyls. Reference Hieber 1931.
Fe(CO)5
FeH(CO)4
Cr(CO)6
CoH(CO)4
Ni(CO)4
Mo(CO)6
W(CO)6
Comment: “Diese sind in der beständigen Carbonylen und Carbonylwasserstoffen zu stabilen 18er-Schalen zusammengetreten…
They make psevdo- noble- gas outer shell- structures. “Und dass man das Metall als 0-werig ansehen muss”
and then the pity: “Die zerstörende Wirkung von Wassergas auf Eisen zb in Gasometern mit stark wassergashältigem Leuchtgas.. blablabla…”
It is eating iron you see, and further stainless steel as you can see from the formulas,….
The carbonyls do not dissolve in water, but dissolve easily in gasoline for instance, and distill over and pass through any physical filter and oxidize with air and condens water in the tank into dark brown metal carbonates. Making the brown hairs of the Tiger on the tank, that further clog the carburator allways in the most critical and dangerous situations.
Tigers do not belong in the tank, but they get into there anyway and eat the metals and clog the carburators.
White tigers are quite especially dangerous. Analysis show Zink- carbonate sediments in the carburator after having passed all filters.. That is explainede as Grignards reaction between obscure products from the cracker with freshly galvanized tank waggons.
Sulphide being a catalyst for the formation of carbonyls.
on sulphur:
Galvanized 3/8 Iron chains keep in seawater in the Oslofjord. But slightly further up in Tyrifjorden with Freshwater and silur & fossile vulcanism, they start to eat under the zink layer if there is a hole, until the iron is eaten all through, leaving a dark FeS- mud behind.
That is Fe & Sulphur bacteriæ in the bottom muds of the freshwater relict fjord. .
They make a big feast, probably reducing SO4– from the water to sulphide by ignoring the zink and eating metallic Fe under it quite greedy with proper teeth of Sulphur..
Titanic is now halfway eaten up the same way.
It is “Early life”.(Fe and sulphur bacteriæ)
They eat meteorite iron leaving the nickel and platinum contents behind.
Conclusion:
There is a lot of possible activities and potensials in the universe even where stainless steel has been used, relating to Carbonyls, sulphur, and Cyanide. I see also Fe Nitrosyl discussed.
Thus I believe that wherever you find pure iron and iron ore of any kind in the universe,, it is proof of water, and of early life. CO also playing a role in the system.