Talk:Hydrogen economy
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[edit] Aluminum-Gallium pellets produce hydrogen from water on contact
I stumbled upon this link under another topic, probably Fuel_cell. The article describes a chemical process in which water reacts with aluminum, the latter effectively stripping water molecules of their oxygen and freeing hydrogen. The gallium prevents formation of aluminum oxide film which would stop the continuous reaction. The reaction takes place until either aluminum or water runs out. Does anyone have more information and any thoughts if this should be included in the article? --Khokkanen 18:49, 1 September 2007 (UTC)
Jerry Woodall, a Purdue Discovery Park researcher gives a Flash-assisted lecture about the technology. --Khokkanen 19:00, 1 September 2007 (UTC)
It's a bit of a sham, the way it is presented. There is no such thing as energy from nothing. The fuel cycle is that you put tons of energy into making the aluminum/gallium and then when you drop it into water the hydrogen bubbles out. The round trip efficiency of the process is no better °than the efficiency of ordinary electrolysis. 199.125.109.42 02:56, 28 September 2007 (UTC)
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- Yes, it's a bit of sham as far as comparison to electrolysis efficiency goes, but not as far as storing hydrogen goes. We basically can't store hydrogen because it's so light - even cryogenic liquid hydrogen is like 8 times lighter than water, and it's very expensive to liquefy. Nobody wants to drive a car around in a car attached to a Zeppelin like the LZ 129 Hindenburg, hence the desire to compress a Hindenburg into a few metal pellets that fit in your pocket, and only let the huge genie out of the bottle when it's needed.
- As far as this gallium/aluminum idea goes, it's not that radical. I was in 7th grade chemistry class when my chemistry professor with a rubber glove rubbed mercury chloride(read that page) powder onto a piece of heavy gauge aluminum wire, then dipped it into water, and it started fizzing. Gallium is basically replacing mercury here, except the gallium amalgam melts at a higher temperature than the mercury one. In fact, you could replace mercury and gallium with other low temperature melting alloys, such as Wood's metal, and sometimes I wonder why the chlor-alkali industry that's in so much of a pinch over mercury emissions does not come up with a similar replacement for mercury, by a low temperature melting alloy, based on mostly Ga, In, Bi, Sb, Ge, Cd, Sn, Pb. Most of these metals are very poisonous, including Hg, Cd, Sb, Pb, I don't know about the rest, Sn is probably the safest.(I just looked up Field's metal that's supposedly nontoxic.) Pb/Sn are the cheap ones, but don't melt low enough, so you need Ga and the even more expensive In, or toxic Cd, Hg. You'd probably have to increase the electrolysis temperature too, even up to 70°C. Even partial replacement of mercury could go a long way in reducing emissions, and might be doable in practically all mercury applications, except where mercury's high nobility and corrosion resistance compared to say Sn is necessary. Low melting point is one of the goals, the other one is high hydrogen overpotential for such things as chlor alkali electrolysis, but low hydrogen overpotential for such things as hydrogen generation from aluminum, if that's what you really want to do, if you're goal is really to generate hydrogen here. Because once you got aluminum, there is something better. Because this whole thing heats up like crazy if you generate hydrogen with it, just like a shorted out battery, it wastes a lot of energy as waste heat. What you need is an electrode such as platinum where the hydrogen evolves, and an electrical load that uses up the Al/H2 electrical potential difference, just like a Zn/Cu based battery doesn't heat up, if there is a suitable electrical load present, but if you short it out, or if you just dip Zn directly into a Cu solution, all the energy comes out as waste heat. Actually what you really need is a suitable oxygen anode, with a large surface area / low oxygen overpotential catalyst, so that you don't do the Al/H2 battery to generate hydrogen to burn in a fuel cell that generates electricity with say 50% efficiency, but you get the full Al/O2 battery energy by generating the electricity directly from this chemical reaction of aluminum dissolving at the cathode and atmospheric oxygen absorbing/dissolving at the anode, just like in a metal-air battery, with way over 50% efficiency. In this case you'd need a super high hydrogen overpotential at the molten aluminum amalgam cathode, so that no waste hydrogen evolves, and superlow oxygen overpotential/excellent catalyst where the atmospheric oxygen is absorbed into the solution. The other issue is getting rid of the aluminum hydroxide flake that builds up. Most aluminum/air batteries so far have not been very successful, because they fall very short of the theoretical battery potentials, mostly because of the ohmic resistance of aluminum hydroxide sludge that builds up, and cannot be efficiently recycled/cleaned up/dealt with. Also there is significant self-discharge once the aluminum comes into contact with the electrolyte, and so far the biggest invention is alloying aluminum with tin to increase the hydrogen overpotential, which gives decently low enough self discharge values. Aqueous aluminum battery systems have been tried over and over and over, as highlighted at Europositron . The big issue is the self discharge by hydrogen generation, and the sludge issue, still, because of the high energy density, aluminum/air batteries have found uses for such things torpedos and emergency standby needs, where the electrolyte and aluminum are kept separate from each other until use. A successful aluminum/air battery may also solve the problem of room temperature aluminum electrolysis that might replace the century old Hall-Héroult process, that requires equivalent stoichiometric CO2 emissions, pound per pound of aluminum, therefore negating any kind of aluminum-economy free from greenhouse gas emissions (they are coming up with titanium/boron based oxygen electrodes that generate oxygen and not CO2, but because of increased electrical costs the industry will not even consider them - it's nonsense to stop using carbon in the Hall-Héroult process before we stop burning coal at power plants that give us the extra electricity energy, because in the Hall-Héroult process this energy is used 100% efficiently, while only 35% efficiently at a power plant heat engine.) A new area not completely explored is the Li-ion like organic electrolyte based aluminum/air battery. There are a couple organic/aluminum systems available, as described by Eliezer Gileadi, Electrode Kineticsfor chemists, chemical engineers and materials scientists, p. 560-563, or as described in patent US3997410. He states that in fact it's impossible to plate aluminum from polar solvents, because of the very strong complexation of aluminum inhibits kinetics, but it's very possible to do it from nonpolar solvents. That reversibility of getting aluminum back and forth in and out of an ionic solution at a much lower temperature than cryolite can, might be the key to a successful commercial aluminum/air battery. (Technically you could have an Al/Cryolite/O2 battery, but the 900C temperature requirement makes it uneconomical. )There is still a need to attack the hydroxide/oxide of aluminum and be able to recycle it, which is hard to imagine in a nonaqueous phase, where it should be very insolube (or a heavily polar phase such as HF or H2SO4 or some exotic highly ionic liquids that dissolve aluminum oxide, such as very ionic but very low temperature molten salts.) You can't even imagine an oxygen electrode in a pure organic phase or a system where the oxide is insoluble, how does the aluminum react with the oxygen, does it form a hard coating on the anode, you would need an intermediate ionic redox species that picks up oxygen ions, carries them around in the same organic phase and transfers them to something like a membrane where it meets with aluminum ions, and drops out pure aluminum oxide crystal flakes. This ionic oxygen carrying species should be too sterically or somehow hindered to complexate aluminum ions, or react with them, it should be very oxygen specific. Can you find one? You might be stuck with the need of an aqueous or polar solvent system to dissolve the oxide. One way to tackle this need for a polar electrolyte for the oxide and need for a nonpolar one for the metal might be a two stage system based on Al metal / organic electrolyte / mercury-or other amalgam-ready metal such as gallium separating the organic from aqueous phase, where aluminum can pass moisture free from aqueous to organic phase / acidic or basic aqueous aluminum electrolyte/ oxygen electrode. The issue might be the very slow kinetics of aluminum entering the amalgam from the aqueous side, but if that's not an issue, you got yourself a carbon emission free room temperature aluminum electrolysis system, that can also function as a battery, something that can be miniaturized enough to drop next to each windmill out in nowhere land that are costly to get tied to the grid. You could do a weekly tour to harvest and pick up the slabs of aluminum produced and dish out the recycled oxide from the end users. That's what windmills and solar stations need, an efficient way to stack up piles of fat, piles of energy, and piles of aluminum that can be shipped around in railcars and combusted, with waste oxides recycled back to the windmill/solar stations, or even nuclear stations. This could eliminate the strain that the grid faces, and could allow each power plant to operate at it's best efficiency nonstop instead of having to play the very stressful cat-and-mouse game to try to keep in step with the current market consumption. There is only so much % of grid power that renewables can replace now, once the fraction of energy produced on the grid from renewables goes over say 30%, the grid becomes almost unmanageable, mostly because pumped storage systems run out of storage capacity (damns look big, but they don't store that much energy - the energy content of 1 kg of aluminum is 31 MJ/kg, while damn water at 100 m height is only 0.001 MJ/kg, so a 1 kg (2.2 lb) chunk of aluminum represents 31 tonnes, or 31 cubic meters (1070 cu ft), of water at 100 m (326 ft) height. A fairly small pile of aluminum-mountain could replace all the energy stored in the Hoover Dam. We need a good means to store renewable energy, and hydrogen currently is just not it, it's expensive to store large quantities, while aluminum you can just pile on a skid and stack it outside in the rain/snow/burning desert heat. As you can see from the main article showing the praxair hydrogen infrastructure image, it's hard to stockpile hydrogen cheaply in very large quantities, it requires expensive large volume containers that have to be cooled very close to absolute zero. It'd be hard for the government to keep a hydrogen reserves inventory like it has a crude oil inventory, but it could easily do that with mountains of aluminum. Aluminum is a solid, and it's more expensive to handle than something that flows easily, unless it's in a slurry form, but at least it's cheap to store if it's a solid - make a pile. Currently this process would still not be "economical" compared to the Hall-Héroult process unless mandated by gov't bodies against CO2 emissions, because the reverse Al2O3+E->Al+O2 system requires more electrical energy than the Al2O3+C+E->Al+CO2, especially in a day and age where most of that electric energy is produced by burning C at a low efficiency. But for the future, or even against the TiB2 based Hall-Héroult process, or for lunar oxygen production, such double staged metal/organic/amalgam/aqueous/oxygen production systems might be the answer, including producing aluminum, alkali and alkali earth metals. Silicon and titanium can be obtained by using alkali/alkali earth metals from their gaseous purified fluorides, while Fe can just simply be plated out of a simple metal/aqueous/oxygen solution. Oh and no, you can't get a patent on all this now that it's published under the GFDL, at least not on the main idea, but you can work out the technical details and get a subpatent on those, that you rightfully deserve. I'd highly appreciate a mention of Sillybilly in your patent, and Wikipedia, if you do get a patent. :) I'd highly welcome any advance toward an aluminum economy that solves the issues with renewable energy storage, because a hydrogen economy so far isn't flying well. By the way, there are at least two patents on low temperature alkali metal production, US6368486 as an organic electrolyte way, and US6730210, a metal/alkali ion conducting membrane/aqueous/oxygen, but not the metal/organic/amalgam/aqueous/oxygen system. Actually, now that I looked it up more, there are references to refining alkali metals from amalgams using organic solvents, such as Journal of Applied Electrochemistry, Vol.5. No. 4 Nov. 1975 p.279-290, but I don't see any of this applied to aluminum in organic solvents. It's just an idea, there might be issues such as aluminum not entering the amalgam at all (if you electrolyze aluminum sulfate with a mercury electrode, do you get an amalgam similar to calcium/sodium, or just a lot of hydrogen/what's the ratio of waste hydrogen to aluminum amalgamated. There are ways to increase hydrogen overpotential, as done with additives to metal acid picking baths, that remove rust but don't fizz hydrogen, such as acetylenes that bind to high energy sites on a metal surface, and reduce waste hydrogen generation) Also, the NASA lunar oxygen production challenge is about to run out of time, if you're quick (two months), you can still beat the deadline, if you can toss together something that generates 5 kg oxygen in 8 hours from lunar dust (basically volcanic rock powder) and it's portable. That sounds like such a basic, simple thing to ask for, especially in this day and age, yet it's so complicated. You probably need an HF/H2SO4 digester that drives the SiF4 and TiF4, ZrF4, etc. into the vapor phase, and leaves you with Al/Ca/Na/Mg/Fe-SO4/SiF6 in aqueous that you can tackle with the above described process. The issue might be CaSO4/CaF2/Na2SiF6 and similar compound solubility that requires complexers to drive into solution, but you can't use ammonia to keep CaF2 in solution, at least not with a mercury electrode, because of an ammonia mercury amalgam that forms (other liquid metals such as gallium might be ok with ammonia.) The SiF4/TiF4/ZrF4 gas phase can be separated by programmed thermal desorption of something like Na2SiF6, Na2TiF6, that have different decomposition temperatures (the best system has to be investigated, whether it's NaF, or KF, or LiF, or even BaF2, or who knows), then the pure fluorides can be reacted with alkali metals to produce the pure Si for solar cells, and Ti, Zr for other uses. This process would be completely closed, with no waste effluents, the only effluents being the MOx->M+O2 metal and oxygen reaction products, while the fluorine, sulfate, organics, water, solubilizing complexers, everything else recycled. Teflon would handle most of your vessel needs as long as low temperature reactions are involved, meaning a relatively light module can be taken up to the moon and it might lasts months or even a few years, unlike the molten magma electrolysis, or similar high temperature ideas, where your vessel is consumed pretty much in a few weeks. The high temperature reactions such as Na/SiF4 bomb reaction vessels might have to be built up and periodically replaced locally on the moon, from Fe/Ti/Ni or similar materials that resist alkali metal/SiF4 corrosion. Unless you can find a room temperature way, maybe a highly energetic organic electrolyte way, to tackle SiF4 into metallic silicon. There are reports of metallic silicon deposition at near room temperature from organic solvents such as one with a 4 V electrochemical window, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, ISBN 3527312390 p602, but this technology seems in a more exotic and rudimentary phase than the aluminum/organic/amalgam one. However electrodepositing thin layers of solar grade silicon at room temperature could drive the cost of solar power through the floor. Silicon is the bulk material in most rocks, next is aluminum, the remaining are more like minor constituents. Currently the best process NASA has is electrolyzing silicon free aluminum/other metal oxides into molten aluminum, treating fresh rock with this molten aluminum to get a molten aluminum/silicon alloy that precipitates out silicon crystals upon cooling to a lower temperature, where the crystals can be centrifuged (imagine a centrifuge spinning high temperature liquid aluminum/silicon, ickk..), then the silicon depleted molten aluminum/silicon liquid alloy recycled for processing more silicates. The whole thing doesn't sound like a very tasty idea, but the situation is dire, trying to process magmatic rocks. For tackling these rocks there is also the more conventional method of carbochlorination/SiCl4 distillation and CO recycling into carbon or hydrocarbons, which might be the most suitable method overall, operating near 800C, even more suitable than low temperature acid digestion/amalgam electrolysis. One has to look at all the options. For low complexity/economic efficiency one would like to just get just the oxygen out of lunar rocks, without dealing with the issues of separating all the other metals out in high purity, but most likely that will be impossible with any kind of chemical processing where you have to add something to the rock, such as a melting point lowering substance, because the only way to guarantee that the additives are recycled is to output only very high purity metals and very high purity oxygen. Sillybilly (talk) 08:57, 22 March 2008 (UTC)
- I've been thinking about this, since I wrote this here, and have to write this down before it escapes my mind, because I'm about to be thinking about something else :). The very same reasons that make impossible to plate aluminum out of polar organics might make it impossible to plate it out from aqueous (even into an amalgam.) The activation energy to de-solvate the very small and very highly charged Al3+ is very high. Technically, there is a way to climb any hill, there is a way to surpass any activation energy, you just have to push harder. In case aluminum doesn't plate into the amalgam at say 4V, try 6V, 10V, 20V. Something's gotta give, or do you only get more fizzing, more hydrogen. If all you get is more fizzing, more hydrogen, then you need to get an even more molecularly smooth surface devoid of any high energy sites and crevices, that makes hydrogen bubble formation more impossible, and use additives, such as acetylides, to cover up the sites that still show up. I think lead has an even higher hydrogen overpotential than mercury, at least I recall sawing it on a graph somewhere, I don't really understand why solid lead compared to molten, molecularly smooth mercury, would be better. But there must be a reason why we have lead acid batteries, and even those fizz some, not too much, but newer generation ones fizz even less, because of the alloy they are made of, and I'm not sure about the additives. So anyway, find the best overpotential amalgam for aluminum, take the voltage through the roof, and see if you can get the aluminum out of solution. Of course if it takes 10V to get an aluminum amalgam, that nixes the technology, because of the energy losses, using 10V to get something that's able to return 1.66 V, charge per charge, but it's important to know what happens. By the way aqueous titanium solutions, that deal with a highly charged and even smaller Ti4+ ion, must have similar issues to aluminum. So any solution to aluminum's issues might be directly applicable to titanium (except titanium doesn't form mercury amalgams like aluminum does, but it might be possible to corrode/alloy with with gallium based liquids.) There might be another way to deal with the situation, without an amalgam. In case titanium is solvent extracted into a water-free organic medium, and from there extracted/stripped from its highly solvating ligands by force (not by pH changes, but by say, using copper or some other metals with higher affinity to those ligands), once you get titanium into a "naked" form, it might be possible to electrodeposit even titanium at room temperature, from organic liquids.
- Should aluminum be impossible to work with, there is another candidate, magnesium. Magnesium should amalgamate fine, being much less charged, should have less kinetic issues with plating out of solution (I think Davy first made calcium metal by amalgam electrolysis of calcium hydroxide, then distilling the 99.5% mercury off, so amalgam electrolysis works with alkaline earth metals, should work with magnesium too.) Magnesium is pretty much the most electropositive metal that still survives being stacked in a pile and not corroding away in no time, though it's a bit more dangerous than aluminum, because if it melts, it burns intensely, and there are a lot of industrial magnesium fires, but less aluminum fires. Lithium is off the list of stackables, because it corrodes quickly, though special coatings such as wax or mineral oil coatings might solve that issue (potassium is kept under kerosene in labs, maybe one needs tanks full of such liquids to keep the lithium mountains under.) The biggest downside of lithium is the abundance problem, it's expensive because it's a relatively rare element. You can make a magnesium mountain cheaply next to each windmill/solar station, but you can't make lithium mountains, there isn't that much lithium around the world. The downside of magnesium is that it has less energy density than aluminum, both volume and weight, however lithium has a much higher energy density by weight (though if you consider the oxide, the recyclable weight per energy gained is high for lithium, because, on a percentage basis, there is more oxygen in lithium oxide, than in aluminum oxide, or magnesium oxide.) A lithium/air battery by the metal/organic/amalgam/aqueous/oxygen system should be the easiest to prototype at present time, because the organic part is so well studied for lithium ion batteries. Then there could be a move to magnesium, to find suitable organic systems for that too. (Note that distilling the mercury out of an amalgam is unfeasible, because 99.5% of the weight has to be distilled to get 0.5% of the primary metal, but organic stripping/electroysis is feasible.)
- As far as lunar oxygen goes, even if aluminum is impossible to amalgamate, calcium is, and then a reaction between dry AlF3 containing materials and either Mg or Ca get yield the Al, but then we're back to electrolyzing cryolite-type high temperature issues, but at least the Ca reduction at high temperature can be done in a bomb, in a simple way, and the sophisticated electrolysis and separation technology could be done at low temperature. Sillybilly (talk) 12:42, 24 March 2008 (UTC)
- Low temperature aqueous processes may never be economically competitive with molten salt processes, simply because of cell resistances/energy efficiencies. In that case it might be a good idea to have molten salt metal-air batteries next to pump storage stations, operating conventional electrolytic high temperature metal processing of magnesium (or aluminum), though they can't use chlorides, but need molten fluoride mixtures instead. When the pumped storage dam is full of water, drain half of it and make a magnesium mountain + pure oxygen, then when the levels stay low for a long period, shut the water flow, and consume the reserve metals in large scale metal-air batteries. This way you don't need to shuffle magnesium ingots around too much, and molten magnesium can be pumped as a liquid. This way you expand the grid capacity, make it more manageable, and renewables might be able to take up 100% of the grid supply because there is enough energy-room for longterm fat storage. Besides crude oil reserves, the gov't could update magnesium reserves, stored easily in big piles. For automotive/mobile applications, where you have to disconnect from the grid, current Li-ion batteries and compressed hydrogen should be able to replace gasoline engines, except people would have to get used to making more frequent pit stops, say every 50-100 miles instead of 150-300 today. That's not a big deal. Li-ion gets 95% efficiency in energy conversion, but hydrogen even with a fuel cell is way under 50%, while with a very simple internal combustion engine it's under 35%, but at least you can carry some decent energy density around with you, in an environmentally friendly way, because lithium ion is not very energy dense, due to the electrolyte/oxidizer. Still, metal/air batteries in a car would give well over 50% grid to wheel efficiency compared to hydrogen/air setups, with decent energy density compared to both hydrogen and li-ion. In a lithium-air system, one would pick up lithium metal at a gas station, and discharge lithium hydroxide. Lithium metal has a much better energy density per weight than either mg or aluminum, and the hydroxide is easier to reprocess, even via the low temperature organic/amalgam way, possibly using In/Ga/Bi/Sn expensive but nontoxic (compared to mercury) low melting alloys. Whether these alloys function at all has to be researched. For instance gallinstan with a -19C melting point wets skin, glass, etc., it's surface tension properties are radically different from mercury. On the other hand, while metal air batteries get a much higher grid to wheel efficiency than compressed hydrogen, the advantage of hydrogen is that the waste products can be vented to the atmosphere, while with metals the downside is that the oxides need to be carried back to the gas station. This is an issue with transportation because the weight increases as the vehicle proceeds on, instead of decreasing, so ultimately the vehicle gains the same weight as if the oxidizer were carried along in the first place. But this is not an issue for grid storage applications, such as pumped storage stations, where long term stable storage of renewable energy (solar, wind) (for up to 5-10 years even) in form of weatherable metal ingots/flakes is more important than the weight issue. Even a zinc/air or iron/air economy might make sense where weight is simply not an issue, because zinc and iron do have ok volumetric energy density, and their aqueous electrolytic processing is simple, no amalgams or organics needed, just high conductivity potassium hydroxide electrolyte with some additives, or an acid based electrolyte that's insensitive even to atmospheric CO2 absorbtion, even if lower conductivity, but easier to store in open air ponds, and water could simply be replenished as it's lost by evaporation. Iron can corrode if stacked, but zinc is resistant, and cheap, and easier to process in aqueous systems than aluminum, lithium or magnesium. The zinc ingots would be heavier and less energy dense mass-wise than any of those other metals, but still they might be the most economical next to a pump storage station, as a metal air battery, or as a renewable energy storage reserve. As long as the energy storage medium does not have to be carried for long distances, such as in an automobile, just locally moved around, as inside a plant environment, the density by mass may not be very important, as long as there is good density by volume, and ease of storage/handling. Pumped storage stations, or in general grid storage stations having to store compressed or liquid or even uncompressed hydrogen is a very expensive proposition, especially on a full year timeframe. So inasmuch as a hydrogen economy is concerned, hydrogen might be a useful temporary intermediate for transportation, but for longterm renewable storage, and grid energy storage one needs an magnesium/aluminum/lithium economy backbone, with government energy reserves vested in them, and a hydrogen economy only for short term transportation energy storage needs. In the 80's the japanese looking at batteries to store large amounts of energy concluded on a high temperature molten sodium/sulfur battery as most cost efficient. Unfortunately sodium and sulfur cannot be extracted from such batteries and stored easily as magnesium, aluminum + oxygen can from either high temperature molten salt/molten metal/oxygen batteries, or if the technology is found and is feasible, low temperature metal/organic/oxygen, or metal/organic/amalgam/aqueous/oxygen sources. (talk) 06:05, 29 March 2008 (UTC)
- The biggest issue with metal/air batteries is efficient removal of the waste oxides, in a concentrated form, so that the electrolyte can be a small quantity, otherwise your overall energy density drops to something very low. Fuel cells can simply emit the waste oxide, the water vapor, while magnesium, aluminum, lithium, and even boron oxide/hydroxides are difficult to emit in a concentrated form. Eltech Research's aluminum-air battery used a pumped electrolyte system with a separate precipitator to remove the aluminum hydroxide jelly, and similar precipitations might be difficult to find with lithium/magnesium. The other method, of leaving the reacted metals superconcentrated in the electrolyte may be more feasible, as, for instance, magnesium sulfate is highly soluble, up to 25% by weight at ambient conditions. Herein lies the beauty of hydrogen and hydrocarbon based energy carriers, inasmuch even liquid CO2 easily separates from the reaction chamber in a very concentrated form, and can be recycled, as a liquid, as opposed to having to deal with solid effluents. My earlier idea of a fuel cell that outputs high pressure liquid CO2 waste that's recycled at power stations(solar stations, windmills) into hydrocarbons might be the most feasible, compared to even liquid ammonia, that's more expensive to make than making a hydrocarbon from CO2. Having to scrub the 0.03% CO2 out of the atmosphere, like plants do, doesn't sound like a feasible solution compared to recycling liquid CO2, unless you can prove me wrong on this. Liquid CO2 is much easier to deal with than either supercompressed hydrogen or liquid hydrogen. We could attack the energy storage problem on the recycling side, and stay with the current hydrocarbon/air systems as energy carriers. We're just not used to carbon sequestration and CO2 recycling from inside an engine, especially while mined hydrocarbons are so cheap, and emitting CO2 is so cheap. Liquid hydrocarbons(diesel, gasoline) are easily pumped, and relatively easily stored as government crude oil reserves, they occupy the sweet spot in the energy density diagram both in terms of weight and volume though for renewable energy storage the whole current engine technology would have to change. Hybrid-like electric cars would have to replace their conventional gasoline engine with direct methanol/ethanol/hydrocarbon based fuel cells, that emit the water but capture the liquid CO2 into a separate compartment, maybe even the same gasoline tank as a separate liquid phase, and then at a gas station the liquid CO2 would get unloaded at the same time that the hydrocarbon/methanol is loaded. This would be an absolutely zero carbon emission vehicle, with an easily recyclable oxide (carbon dioxide) to windmills, power stations. Imagine a steel cylinder of liquid CO2 next to each windmill, and a device that generates hydrocarbons from the CO2 + H2O +electricity. On your weekly harvesting tours you could tap the supernatant or undernatant hydrocarbon honey from these cylinders, and while refilling them with fresh CO2. Liquid carbon dioxide is just so nice to work with, so much easier to deal with than liquid hydrogen, because it stores at relatively low pressure at room temperature, and it's better than the similarly liquefiable liquid ammonia, because that's expensive to make, and it's toxic, and has an odor problem. The worst imaginable accidents with liquid CO2 would have zero environmental impact, other than the freezing/suffocation of nearby people. Gasoline, ammonia, liquid hydrogen, compressed hydrogen, methane are all more dangerous, while magnesium/aluminum is the safest, but can get dangerous if it catches fire. The CO2 losses due to accidents and leaks that are low energy waste so a not a big deal, can be made up by life-based carbon sources, but currently all life on the planet functions at about 70-100 TW compared to humanity's 15TW need, so a fully biodiesel/ethanol based economy is not feasible, we have to find a direct way to get to the solar energy, via windmills/solar stations, and then store this energy into something. If you only have to "make up" for CO2 losses, say a 0.1TW-0.5TW compared to a global 60TW consumption in 50 years, that's very possible to do life-based. The tools and methods in organic chemistry are so vast, that I have no fears that low temperature carbon dioxide reduction to fat-like hydrocarbons is possible, if nothing else, we know it's possible because life is doing it at 37°C. And life also figured out a way to combust the hydrocarbons at low temperatures with sophisticated catalysts - perhaps a non-fuel cell low temperature hydrocarbon-air battery is possible, something that Tesla used to dream about, that would give much better than 30% energy converstion currently in gasoline engines, or even 50% as in fuel cells. We can't make such sophisticated catalysts and enzymes, but as a starting point, superacids protonate and dissolve even candlewax, put it into a highly reactive state, and you can go from there. And we don't necessarily need the energy density of fat, simply non-bio CO2 derived ethanol, or methanol might suffice. It should be relatively easy to make methanol out of CO2. So so much for using hydrogen or aluminum as a hydrogen storage medium, or a metal air battery, we've been through this so much, and we're still back to hydrocarbons. If you can figure out an efficient way to extract in a concentrated form and recycle aluminum/magnesium/lithium oxides, while maintaining the high energy efficiency, and energy density, you might beat compressed hydrogen and liquid CO2-recycling based hydrocarbons. Just how high a concentration of aluminum hydroxide sludge are you making with your gallium or mercury based aluminum digestion, and how do you plan to recycle it, how pumpable is it, compared to liquid CO2? Pumping a liquid is just so much less work than having to haul it around on skids with a lift truck, I know it from first hand experience. One of the reasons that most steam engines were replaced by Diesel engines is that the train engineer doesn't have to shovel the coal anymore (besides having to carry lots of water, which drops the energy density/increases engine cost). Imagine having a Lexus where you have to toss some coal onto the fire while driving, or have a hopper high up in the air that gets stuck periodically from the caking aluminum/magnesium powder, or even a screw that pumps powder from under the car where the gas tank is, and malfuctions. Even most solids today, such as coal and rocksalt are handled like fluids on large scale, while mere mortals like you and I handle these things with a shovel, on small scale. It's a big deal. Dealing with liquids instead of solids is almost an absolute must anymore, as long as those liquids are not gaseous, or too light to store in any meaningful way. Liquid hydrocarbons are in such a sweet spot in all these respects when it comes to storing chemical energy, in their energy density by volume, by weight, being liquid fuel, and gaseous effluent, and most importantly, being able to store them as government energy reserves. In my opinion they are also by far the most ergonomic ways of storing hydrogen, compared to any other means of storing hydrogen. We may have to stick to them, just simply modify the gaseous effluent part, where the carbon emission is concerned, and recycle the carbon oxide. All other means of chemical energy storage have this issue of oxide recycling anyway - except hydrogen and liquid ammonia which have their own special issues - and carbon oxides are hard to beat with respect of ease of dealing with. By the way, coal as a solid fuel beats other solid fuels such as aluminum, magnesium, lithium, boron, lithium borohydride in ergonomics, by the fact that its combustion product is a fluid, not a solid, not a solution, even if this very fluid, CO2 gas, is the greenhouse gas that we're trying to stay away from emitting into the atmosphere. Silicon and aluminum oxides are ubiquitous, not very polluting. Still, can you picture cars going on a highway periodically ejecting chunks of aluminum or silicon oxides, basically clay and sand? What are the safety issues with such flying solids projectiles. Ejecting nothing as with batteries, or ejecting gases, or even liquids is so much better from the ergonomics, user friendly point of view. And by the way, we still use batteries even with gasoline/coal as the main energy carrier. Even if we don't get everything we want from aluminum/magnesium, there is still at least something to research. Namely, the organic electrolyte technology extended to aluminum and magnesium, similar to lithium ion, with conventional non-air anions (hexafluorophosphate or tetrafluoroborate) might drop the battery cost, at least as far as the price of aluminum/magnesium compared to lithium($40+/lb) goes, giving something intermediate in performance between lithium-ion and NiMH. Sillybilly (talk) 09:18, 30 March 2008 (UTC)
- In a world where people could trust each other, and not fear having too much power concentrated in one person's hands, you could have a high pressure confinement fission based nuclear car with a tiny amount of fuel that needs to be refueled every 3 years or so, and in the distant future, star-trek like fusion device based cars. The fission based technology is almost there today, down to a 1 cubic meter size device, but in the wrong hands, with malice, such device can deliver a lot more destruction than the 9/11 airplanes, that only contained so much concentrated chemical energy. Because of the destructive power, and our inability to get people to stop wanting to harm each other, we have to stick to low energy density chemical energy carriers and renewables, and nuclear can only be a temporary ultra high security necessity, while we build up a renewable infrastructure. The gasoline/air combination is pretty much the most concentrated form of chemical energy, hydrogen is about the same, a little more dense weight wise and less dense volume wise, but definitely nowhere near as ergonomic and user friendly as gasoline. Liquid ammonia is less difficult than hydrogen, but more difficult and even less dense than gasoline, and it's expensive. Hydrazine is easier to combust than ammonia, but more toxic and more expensive. Metal/air (same issues as metal/hydrogen) and other batteries are way less energy dense. There is a reason why the most recent ISS space station launch was done with a Soyuz-FG based on, guess what, not liquid hydrogen, but kerosene RP-1. So even where energy per unit mass is of utmost importance, where hydrogen should win hands down, even in rocketry, hydrocarbons are more ergonomic and user friendly than liquid hydrogen, and present a competition to it. It'd be nice if there were something in between chemical energy carrier densities that peak near 50MJ/L and 50 MJ/kg, and nuclear energy carrier densities (that are 50 milion MJ/kg and 1500 million MJ/L), something on the order of 500-5000 MJ/kg would be nice. Unfortunately it's not such a world that we live in, at least we don't know of any such technologies. You could argue that even gasoline is too dangerous, too energy dense in the wrong hands, and lots of very low density lithium ion or similar batteries are the safest, that is, lithium ion battery filled cars are safe against terrorist malice, they cannot be easily used to blow up a building. Unfortunately when it comes to air transportation, airplanes won't stay airborne for long with low energy density fuels, such as lithium ion batteries, which could deliver a 20-40 minute flight, as opposed to gasoline type fuels that go for a few hours to a day (even that's too short), while a nuclear powered airplane could stay airborne for a few years, and only need to be refueled every few years. But I definitely don't want nuclear airplanes flying around, and even gasoline powered ones are a safety issue. For safety we could ban all nuclear power, we could ban airplanes, and institute a 20 mph speed limit on all roads, which would practically eliminate all deaths by car accidents. This is the other extreme side of the safety issue, and people don't want this extreme safety either, they are quite accepting of the risk of death from driving over 40 mph, compared to the economic benefit they derive from it, and if anything, some risk from terrorists will be accepted in the future. There is such a thing as too much safety, there has to be a balance, there is always a balance, that's why I say something on the order of 500-5000 MJ/kg would be nice, because 50 million is definitely too much, even if you find a safe, tamper proof and usable way to dilute it to the 500 MJ/kg range. Unfortunately there are no safe and tamper proof ways, every idiot proof device simply creates a better idiot. There is also limited reserves of high concentration nuclear ores, though there is quite a bit of low concentration material around. The japanese tried ion exchange resins to extract the fuel from seawater, with some success, even if not economically competitive right now. Comparatively, there is plenty of solar energy resource in the world, especially in low bio-intensity deserts ,and also tropical oceans, where the dissolved oxygen concentration is small because of high water temperatures, therefore low bio-intensity, so covering up large areas with solar panels would not reduce too much of the biosphere. Solar resources in deserts are harvestable at about 30-60 W/m2 average with silicon panels, possibly 200W/m2 with ultra high temperature concentrator/noble gas based thermal engines. Both solar and wind lack a suitable longterm chemical storage technology. Currently most renewables are directly connected to the grid, with pumped-hydro storing any excess energy, and the fossil combustion (where the fossils themselves are the storage medium) is throttled. A fully renewable energy based economy will have to figure out the non-fossil based storage, into a chemical energy carrier, which is the biggest show stopper right now, besides cost/profitability issues compared to gasoline. At $3/gal gasoline is still incredibly cheap, because it's so cheap to punch a hole in the ground, and collect the high energy density honey into barrels. Once you have to roll up your sleeves and actually generate that high energy density honey, then collecting it into a barrel becoming a very small and insignificant aspect of the process, the price of such energy carrier will skyrocket. Same issues with coal/aluminum/magnesium. The current 5cents/kWh from Kentucky coal is unsustainable once that reserve runs out, 50 cents/kWh sounds much more reasonable. There is about 200 years worth of Kentucky coal reserve around, but we can't extract all that coal and dump it into the atmosphere, because of greenhouse effects that we cannot predict. These effects may or may not be as bad as scientists say, but it could be even worse, even desertifying the Kentucky coal areas in 100 years - Lake Chad is gone from world atlases, and Niger has incredible drout/famine already. Banning freon to save the ozone layer was a no brainer, because there were even cheaper and just as well performing replacements available. Banning fossils to stop desertification/sea level rise is a totally different story, because any replacement is an order of magnitude more expensive (even if wind is as low 3c/kWh, its longterm chemical energy storage is an order of magnitude more expensive). A freewheeling extraction-cost-only-based free market economy will dump all that Kentucky coal into the atmosphere, and only stop the destruction before it's too late. That's why government intervention regulating fossil consumption is necessary, which will automatically drive energy costs even higher, and be very unpopular. I want to see the politician that survives such measures. I don't envy any of the candidates. Don't shoot the messenger? How about the slogan: Folks, the age of cheap coal and oil is over, we have to tighten the belt more, and ask all citizens to sacrifice. Hahaha. Poor candidates. Sillybilly (talk) 11:16, 4 April 2008 (UTC)
- I've started looking into carbon dioxide reduction at low temperature. It turns out there is active research already in this very topic, there are a few transition metal complexes (such as cobalt phthalocyanine) that can electrocatalitically and selectively reduce carbon dioxide to carbon monoxide, methane or formic/oxalic acid (depending on the catalyst) instead of hydrogen from water, up to 98% galvanic efficiency (though overpotential is an issue). Carbon monoxide is relatively easy to react to form a wide range of organic chemicals. A windmill could electrocatalitically reduce carbon dioxide to carbon monoxide, then generate hydrogen, and from the two, methanol or ethanol. Non-bio-derived ethanol is like a dream, both as safety, environmental and ergonomic user friendliness. It could replace all the natural gas pipelines, and would be much safer to pipe into a home, where it could be used as food, cleaner, solvent or fuel. As far as solar stations go, they might go with the same technology as windmills, but there might be a way to use solar energy directly to activate a catalyst into a high energy state, which then effectively reduces carbon dioxide, without having to generate electricity first, though the light absorption/quantum efficiency may not be good. If a carbon dioxide reduction catalyst is selective enough, it might be able to deal with direct atmospheric CO2, or slightly preconcentrated CO2, by ethanolamine and such carbon dioxide scrubbers, eliminating the need to recycle the relatively difficult and high pressure liquid CO2. Sillybilly (talk) 13:54, 4 April 2008 (UTC)
- There is already an initiative] to reduce CO2 to CO simply by using high temperature from solar energy. Sillybilly (talk) 17:07, 26 April 2008 (UTC)
- One of the big problems in replacing/complementing life to scrub CO2 out of the atmosphere using solar energy is that you run into the same issues that life runs into, namely the need for water. This is no problem with a windmill near a river, but a windmill doesn't have sophisticated roots to suck up water from the ground far from water sources. It's a real big problem in a desert, if you had a water pond with solar absorbing dies that scrub CO2 out of the atmosphere and generate CO, because you'd lose the water from the pond. Cactuses are experts at retaining water, but it takes too much technology for us mere mortals to scrub atmospheric CO2 in a desert, unless we use something like low vapor pressure DMSO based solutions, or even things like mineral oil. In a desert moisture free, alien looking low vapor pressure things, such as high vapor pressure organics(environmental issues) carbon recyclers, liquid CO2 recyclers, or molten salt(fluoride) based metal/air battery setup might sound like more of an ideal fit, than water based systems that mimic life, and do the same thing as life. If anything, microbes that produce methane out of CO2 are cheaper than any technology we can come up with, even in deserts. Photosynthesys is about 0.2-2% efficient, while silicon solar panels are 10-15%, so life alone won't cover the world's energy needs, it has to be better than life. Also in a desert it's nonsense to put up huge CO2 scrubbing ponds, and then solar panels next to them, you'd have to have to light absorbing materials right in your pond, and the cheapest technology right now is algea, or life. Finding an artificial catalyst that beats life in this efficiency, and deivers something on the order of 10% light to CO or CH4, that's a far shot. So it's basically desert farming, with all its drout problems. At first I was thinking about a plastic cover over the ponds, but to simply let the CO2 in you need to bubble or contact the water with air, and then you simply lose your water vapor. What you need is something that contacts the CO2 without contacting the air, some low density organic that floats on top of water in a thin layer, and dissolves carbon dioxide, but retards water evaporation. Something like octanolamine instead of ethanolamine, or dodecyl-diamine, or something similar. This way you could farm in deserts too. Basically in deserts right now the most feasible storage technology is the same as lunar oxygen mining, the creating of silicon, aluminum, magnesium metals, calcium oxide/cement, sodium hydroxide and titanium dioxide. You simply can't get liquids out of deserts, even if liquids are so ergonomic, getting them is very much not ergonomic. The biggest output in a desert should be silicon, solar grade, and if the price is cheap enough, and it's produced in massive quantities from desert sand, then all construction surfaces in the world covered with it, every house, every roof, every building, nontransparent or semitransparent. In deserts solar concentrators are probably most efficient and economical, but off in the middle of the pacific ocean, you can't have conentrators, because of the waves moving your mirrors. You could still have massive semi-transparent silicon panel arrays combined with wave energy harvesters, that pipe the electricity into an ultrahigh voltage dc line (700,000 volts) that send the electricity to the mainland to be processed. Piping hydrogen might be another alternative. In none of these solar setups does getting hydrocarbons fuels back sound like a feasible solution, the only options are metals, hydrogen, or liquid ammonia. Sillybilly (talk) 20:40, 5 April 2008 (UTC)
- Desert farming is difficult because of drought issues, but looking at the Solar land area.png image there are extremely large oceanic areas with powerful solar influx that shouldn't have a drought problem. The biointensity/photosynthetic activity is fairly limited - looking from outer space oceans are mostly blue, not green, while the land areas with high solar influx are either desertous or very biointense rain forest like. Photosynthetic life is currently the cheapest and highest high tech means of storing solar energy into a hydrocarbon form, however its efficiency is on the order of 0.2%, while desert concentrating thermal or photovoltaic provides over 10% easily, though at very high cost. Profitability wise life might be the cheapest. Most large green/biointense areas are also located in areas such as Northern America and Europe/Russia, of low solar influx. There should be a way to massively increase the 100 TW that life functions at by turning large areas of the oceans green, by floating ponds of algea to get algae fuel. Liquid farming should probably be cheaper largescale than current land based crop farming, simply because of the handling solids vs. liquids issue. Huge tanker ships could filter the green biomass from the oceans, and the major food item in the world could change to seaweed from rice, corn and soybean. Whether the biomass from seas are used as fuel or food, it is practically the same issue. Large human populations or high standards of living are only sustainable by a large energy supply. This sea farming is a very dangerous game though, because it could totally upset the global climate, because of changes in reflectivity/ocean current temperatures. It might turn the Sahara desert into a rainforest, and desertify areas like India. We don't know. But extra farming could alleviate the global food vs fuel problems. Simple concentrating thermal and photovoltaic solar energy devices in deserts should have much less of an impact on the climate, but the cost of building up and maintaining the large areas are enormous, while life simply multiplies up to cover the areas needed and takes care of the maintenance itself. Why the oceans are not all already green is probably because of a limiting nutrient problem, probably phosphates. If I recall that's the reason why phosphates are banned from detergents, they "devastate" freshwater lakes by "eutrophication" into "green deserts" of algea, making life impossible for other lifeforms such as fish. But a far as the global energy crisis and food vs fuel crisis is concerned "green deserts" should be a solution, not a problem. There are photosynthesizing species of algea or other green lifeforms that thrive just fine in saltwater conditions, unlike most land plants, that need desalination to even irrigate in desert areas. There should be a way to create massive floating ponds of proper nutrition on top of the oceans, harvest the green biomass, extract the hydrocarbons, and return the ash-nutrition to the ponds. The pumping energy needed for filtering out the green biomass could be driven by ocean thermal power devices, based on temperature differences between surface and deep water regions, possibly further upsetting oceanic currents and global climate, or just using a fraction of the harvested energy to drive the filtering pumps, as whales do to filter out the plankton. Or having a species that generates methane, or, ideally, propane/butane, would eliminate much of the need to filter on large scale, but it is difficult to collect gases from enormous areas, and to provide incoming CO2 at the same time, because of very dilute methane concentration. Escaping methane would aggravate global warming issues, so it's probably best to stick to species that simply produce O2 and retain all the carbon within their own biomass, instead of emitting portions as hydrocarbons. Having a nutrition limited species, a species with an Achilles heel would ensure that greenness of oceans is controllable, and it doesn't get out of hand, but there is a danger of genetically engineered species that thrive in almost no nutrition zones, tightly holding on to the nutrition like cactuses tightly hold on to water. Such a species escaping from the farming ponds might turn all the oceans green, so biotechnology is very dangerous in this sense. If such specie gets too successful, they might drive the global atmospheric CO2 content too low, and become a danger to land based life such as rainforests and regular food crops by CO2 starvation. So any such biotech improvement would have to start on the safety side, of providing a proper predator that can keep things from getting out of hand, that would thrive in "green algea deserts", and provide a balancing factor, an ecosystem against things getting out of hand. A predator such as a fish that upgrades the energy density into fat from wet carbohydrates may also be more economical from the filtration/extraction point of view, because filtering fish out of seawater is cheaper than filtering/drying seaweed, but pumping gasoline at a gas station that came from killing tons of fish feels inhumane, just like fish used as fertilizer seems inhumane, even though salmon scattered around in forests by grizzlies are a key fertilizer in their relevant ecosystems, and without them that whole ecosystem might collapse, but possibly be replaced by another ecosystem that's more "humane" and pleasing to animal rights activists. What's, ethical, what's right and wrong is hard to tell. We do have a choice in how we live, and simply filtering out plants might be the more ethical means to live, at least as far as fuel goes, and animal life reserved as food only. There is also a lot of energy waste going into maintaining a predator, so the total harvestable energy from a given area might drop too much during the upgrade to fat from carbohydrates. A largescale but controllable intensity ocean farming might also be a means of controlling atmospheric CO2 concentrations, fixing the global warming issues. It is very difficult to predict the climate effects of such largescale changes. There is also the issue of economics, of scarcity, or property, who owns what areas of the oceans, once they become a valuable resource. The oceans currently have an overfishing problem because of the tragedy of the commons. Sillybilly (talk) 13:02, 9 May 2008 (UTC)
- A quote from Algae_fuel#Biodiesel_production: Microalgae have much faster growth-rates than terrestrial crops. The per unit area yield of oil from algae is estimated to be from between 5,000 to 20,000 gallons per acre, per year (4.6 to 18.4 l/m2 per year); this is 7 to 30 times greater than the next best crop, Chinese tallow (699 gallons).Sillybilly (talk) 23:03, 18 May 2008 (UTC)
- Desert farming is difficult because of drought issues, but looking at the Solar land area.png image there are extremely large oceanic areas with powerful solar influx that shouldn't have a drought problem. The biointensity/photosynthetic activity is fairly limited - looking from outer space oceans are mostly blue, not green, while the land areas with high solar influx are either desertous or very biointense rain forest like. Photosynthetic life is currently the cheapest and highest high tech means of storing solar energy into a hydrocarbon form, however its efficiency is on the order of 0.2%, while desert concentrating thermal or photovoltaic provides over 10% easily, though at very high cost. Profitability wise life might be the cheapest. Most large green/biointense areas are also located in areas such as Northern America and Europe/Russia, of low solar influx. There should be a way to massively increase the 100 TW that life functions at by turning large areas of the oceans green, by floating ponds of algea to get algae fuel. Liquid farming should probably be cheaper largescale than current land based crop farming, simply because of the handling solids vs. liquids issue. Huge tanker ships could filter the green biomass from the oceans, and the major food item in the world could change to seaweed from rice, corn and soybean. Whether the biomass from seas are used as fuel or food, it is practically the same issue. Large human populations or high standards of living are only sustainable by a large energy supply. This sea farming is a very dangerous game though, because it could totally upset the global climate, because of changes in reflectivity/ocean current temperatures. It might turn the Sahara desert into a rainforest, and desertify areas like India. We don't know. But extra farming could alleviate the global food vs fuel problems. Simple concentrating thermal and photovoltaic solar energy devices in deserts should have much less of an impact on the climate, but the cost of building up and maintaining the large areas are enormous, while life simply multiplies up to cover the areas needed and takes care of the maintenance itself. Why the oceans are not all already green is probably because of a limiting nutrient problem, probably phosphates. If I recall that's the reason why phosphates are banned from detergents, they "devastate" freshwater lakes by "eutrophication" into "green deserts" of algea, making life impossible for other lifeforms such as fish. But a far as the global energy crisis and food vs fuel crisis is concerned "green deserts" should be a solution, not a problem. There are photosynthesizing species of algea or other green lifeforms that thrive just fine in saltwater conditions, unlike most land plants, that need desalination to even irrigate in desert areas. There should be a way to create massive floating ponds of proper nutrition on top of the oceans, harvest the green biomass, extract the hydrocarbons, and return the ash-nutrition to the ponds. The pumping energy needed for filtering out the green biomass could be driven by ocean thermal power devices, based on temperature differences between surface and deep water regions, possibly further upsetting oceanic currents and global climate, or just using a fraction of the harvested energy to drive the filtering pumps, as whales do to filter out the plankton. Or having a species that generates methane, or, ideally, propane/butane, would eliminate much of the need to filter on large scale, but it is difficult to collect gases from enormous areas, and to provide incoming CO2 at the same time, because of very dilute methane concentration. Escaping methane would aggravate global warming issues, so it's probably best to stick to species that simply produce O2 and retain all the carbon within their own biomass, instead of emitting portions as hydrocarbons. Having a nutrition limited species, a species with an Achilles heel would ensure that greenness of oceans is controllable, and it doesn't get out of hand, but there is a danger of genetically engineered species that thrive in almost no nutrition zones, tightly holding on to the nutrition like cactuses tightly hold on to water. Such a species escaping from the farming ponds might turn all the oceans green, so biotechnology is very dangerous in this sense. If such specie gets too successful, they might drive the global atmospheric CO2 content too low, and become a danger to land based life such as rainforests and regular food crops by CO2 starvation. So any such biotech improvement would have to start on the safety side, of providing a proper predator that can keep things from getting out of hand, that would thrive in "green algea deserts", and provide a balancing factor, an ecosystem against things getting out of hand. A predator such as a fish that upgrades the energy density into fat from wet carbohydrates may also be more economical from the filtration/extraction point of view, because filtering fish out of seawater is cheaper than filtering/drying seaweed, but pumping gasoline at a gas station that came from killing tons of fish feels inhumane, just like fish used as fertilizer seems inhumane, even though salmon scattered around in forests by grizzlies are a key fertilizer in their relevant ecosystems, and without them that whole ecosystem might collapse, but possibly be replaced by another ecosystem that's more "humane" and pleasing to animal rights activists. What's, ethical, what's right and wrong is hard to tell. We do have a choice in how we live, and simply filtering out plants might be the more ethical means to live, at least as far as fuel goes, and animal life reserved as food only. There is also a lot of energy waste going into maintaining a predator, so the total harvestable energy from a given area might drop too much during the upgrade to fat from carbohydrates. A largescale but controllable intensity ocean farming might also be a means of controlling atmospheric CO2 concentrations, fixing the global warming issues. It is very difficult to predict the climate effects of such largescale changes. There is also the issue of economics, of scarcity, or property, who owns what areas of the oceans, once they become a valuable resource. The oceans currently have an overfishing problem because of the tragedy of the commons. Sillybilly (talk) 13:02, 9 May 2008 (UTC)
- One of the big problems in replacing/complementing life to scrub CO2 out of the atmosphere using solar energy is that you run into the same issues that life runs into, namely the need for water. This is no problem with a windmill near a river, but a windmill doesn't have sophisticated roots to suck up water from the ground far from water sources. It's a real big problem in a desert, if you had a water pond with solar absorbing dies that scrub CO2 out of the atmosphere and generate CO, because you'd lose the water from the pond. Cactuses are experts at retaining water, but it takes too much technology for us mere mortals to scrub atmospheric CO2 in a desert, unless we use something like low vapor pressure DMSO based solutions, or even things like mineral oil. In a desert moisture free, alien looking low vapor pressure things, such as high vapor pressure organics(environmental issues) carbon recyclers, liquid CO2 recyclers, or molten salt(fluoride) based metal/air battery setup might sound like more of an ideal fit, than water based systems that mimic life, and do the same thing as life. If anything, microbes that produce methane out of CO2 are cheaper than any technology we can come up with, even in deserts. Photosynthesys is about 0.2-2% efficient, while silicon solar panels are 10-15%, so life alone won't cover the world's energy needs, it has to be better than life. Also in a desert it's nonsense to put up huge CO2 scrubbing ponds, and then solar panels next to them, you'd have to have to light absorbing materials right in your pond, and the cheapest technology right now is algea, or life. Finding an artificial catalyst that beats life in this efficiency, and deivers something on the order of 10% light to CO or CH4, that's a far shot. So it's basically desert farming, with all its drout problems. At first I was thinking about a plastic cover over the ponds, but to simply let the CO2 in you need to bubble or contact the water with air, and then you simply lose your water vapor. What you need is something that contacts the CO2 without contacting the air, some low density organic that floats on top of water in a thin layer, and dissolves carbon dioxide, but retards water evaporation. Something like octanolamine instead of ethanolamine, or dodecyl-diamine, or something similar. This way you could farm in deserts too. Basically in deserts right now the most feasible storage technology is the same as lunar oxygen mining, the creating of silicon, aluminum, magnesium metals, calcium oxide/cement, sodium hydroxide and titanium dioxide. You simply can't get liquids out of deserts, even if liquids are so ergonomic, getting them is very much not ergonomic. The biggest output in a desert should be silicon, solar grade, and if the price is cheap enough, and it's produced in massive quantities from desert sand, then all construction surfaces in the world covered with it, every house, every roof, every building, nontransparent or semitransparent. In deserts solar concentrators are probably most efficient and economical, but off in the middle of the pacific ocean, you can't have conentrators, because of the waves moving your mirrors. You could still have massive semi-transparent silicon panel arrays combined with wave energy harvesters, that pipe the electricity into an ultrahigh voltage dc line (700,000 volts) that send the electricity to the mainland to be processed. Piping hydrogen might be another alternative. In none of these solar setups does getting hydrocarbons fuels back sound like a feasible solution, the only options are metals, hydrogen, or liquid ammonia. Sillybilly (talk) 20:40, 5 April 2008 (UTC)
- In a world where people could trust each other, and not fear having too much power concentrated in one person's hands, you could have a high pressure confinement fission based nuclear car with a tiny amount of fuel that needs to be refueled every 3 years or so, and in the distant future, star-trek like fusion device based cars. The fission based technology is almost there today, down to a 1 cubic meter size device, but in the wrong hands, with malice, such device can deliver a lot more destruction than the 9/11 airplanes, that only contained so much concentrated chemical energy. Because of the destructive power, and our inability to get people to stop wanting to harm each other, we have to stick to low energy density chemical energy carriers and renewables, and nuclear can only be a temporary ultra high security necessity, while we build up a renewable infrastructure. The gasoline/air combination is pretty much the most concentrated form of chemical energy, hydrogen is about the same, a little more dense weight wise and less dense volume wise, but definitely nowhere near as ergonomic and user friendly as gasoline. Liquid ammonia is less difficult than hydrogen, but more difficult and even less dense than gasoline, and it's expensive. Hydrazine is easier to combust than ammonia, but more toxic and more expensive. Metal/air (same issues as metal/hydrogen) and other batteries are way less energy dense. There is a reason why the most recent ISS space station launch was done with a Soyuz-FG based on, guess what, not liquid hydrogen, but kerosene RP-1. So even where energy per unit mass is of utmost importance, where hydrogen should win hands down, even in rocketry, hydrocarbons are more ergonomic and user friendly than liquid hydrogen, and present a competition to it. It'd be nice if there were something in between chemical energy carrier densities that peak near 50MJ/L and 50 MJ/kg, and nuclear energy carrier densities (that are 50 milion MJ/kg and 1500 million MJ/L), something on the order of 500-5000 MJ/kg would be nice. Unfortunately it's not such a world that we live in, at least we don't know of any such technologies. You could argue that even gasoline is too dangerous, too energy dense in the wrong hands, and lots of very low density lithium ion or similar batteries are the safest, that is, lithium ion battery filled cars are safe against terrorist malice, they cannot be easily used to blow up a building. Unfortunately when it comes to air transportation, airplanes won't stay airborne for long with low energy density fuels, such as lithium ion batteries, which could deliver a 20-40 minute flight, as opposed to gasoline type fuels that go for a few hours to a day (even that's too short), while a nuclear powered airplane could stay airborne for a few years, and only need to be refueled every few years. But I definitely don't want nuclear airplanes flying around, and even gasoline powered ones are a safety issue. For safety we could ban all nuclear power, we could ban airplanes, and institute a 20 mph speed limit on all roads, which would practically eliminate all deaths by car accidents. This is the other extreme side of the safety issue, and people don't want this extreme safety either, they are quite accepting of the risk of death from driving over 40 mph, compared to the economic benefit they derive from it, and if anything, some risk from terrorists will be accepted in the future. There is such a thing as too much safety, there has to be a balance, there is always a balance, that's why I say something on the order of 500-5000 MJ/kg would be nice, because 50 million is definitely too much, even if you find a safe, tamper proof and usable way to dilute it to the 500 MJ/kg range. Unfortunately there are no safe and tamper proof ways, every idiot proof device simply creates a better idiot. There is also limited reserves of high concentration nuclear ores, though there is quite a bit of low concentration material around. The japanese tried ion exchange resins to extract the fuel from seawater, with some success, even if not economically competitive right now. Comparatively, there is plenty of solar energy resource in the world, especially in low bio-intensity deserts ,and also tropical oceans, where the dissolved oxygen concentration is small because of high water temperatures, therefore low bio-intensity, so covering up large areas with solar panels would not reduce too much of the biosphere. Solar resources in deserts are harvestable at about 30-60 W/m2 average with silicon panels, possibly 200W/m2 with ultra high temperature concentrator/noble gas based thermal engines. Both solar and wind lack a suitable longterm chemical storage technology. Currently most renewables are directly connected to the grid, with pumped-hydro storing any excess energy, and the fossil combustion (where the fossils themselves are the storage medium) is throttled. A fully renewable energy based economy will have to figure out the non-fossil based storage, into a chemical energy carrier, which is the biggest show stopper right now, besides cost/profitability issues compared to gasoline. At $3/gal gasoline is still incredibly cheap, because it's so cheap to punch a hole in the ground, and collect the high energy density honey into barrels. Once you have to roll up your sleeves and actually generate that high energy density honey, then collecting it into a barrel becoming a very small and insignificant aspect of the process, the price of such energy carrier will skyrocket. Same issues with coal/aluminum/magnesium. The current 5cents/kWh from Kentucky coal is unsustainable once that reserve runs out, 50 cents/kWh sounds much more reasonable. There is about 200 years worth of Kentucky coal reserve around, but we can't extract all that coal and dump it into the atmosphere, because of greenhouse effects that we cannot predict. These effects may or may not be as bad as scientists say, but it could be even worse, even desertifying the Kentucky coal areas in 100 years - Lake Chad is gone from world atlases, and Niger has incredible drout/famine already. Banning freon to save the ozone layer was a no brainer, because there were even cheaper and just as well performing replacements available. Banning fossils to stop desertification/sea level rise is a totally different story, because any replacement is an order of magnitude more expensive (even if wind is as low 3c/kWh, its longterm chemical energy storage is an order of magnitude more expensive). A freewheeling extraction-cost-only-based free market economy will dump all that Kentucky coal into the atmosphere, and only stop the destruction before it's too late. That's why government intervention regulating fossil consumption is necessary, which will automatically drive energy costs even higher, and be very unpopular. I want to see the politician that survives such measures. I don't envy any of the candidates. Don't shoot the messenger? How about the slogan: Folks, the age of cheap coal and oil is over, we have to tighten the belt more, and ask all citizens to sacrifice. Hahaha. Poor candidates. Sillybilly (talk) 11:16, 4 April 2008 (UTC)
- The biggest issue with metal/air batteries is efficient removal of the waste oxides, in a concentrated form, so that the electrolyte can be a small quantity, otherwise your overall energy density drops to something very low. Fuel cells can simply emit the waste oxide, the water vapor, while magnesium, aluminum, lithium, and even boron oxide/hydroxides are difficult to emit in a concentrated form. Eltech Research's aluminum-air battery used a pumped electrolyte system with a separate precipitator to remove the aluminum hydroxide jelly, and similar precipitations might be difficult to find with lithium/magnesium. The other method, of leaving the reacted metals superconcentrated in the electrolyte may be more feasible, as, for instance, magnesium sulfate is highly soluble, up to 25% by weight at ambient conditions. Herein lies the beauty of hydrogen and hydrocarbon based energy carriers, inasmuch even liquid CO2 easily separates from the reaction chamber in a very concentrated form, and can be recycled, as a liquid, as opposed to having to deal with solid effluents. My earlier idea of a fuel cell that outputs high pressure liquid CO2 waste that's recycled at power stations(solar stations, windmills) into hydrocarbons might be the most feasible, compared to even liquid ammonia, that's more expensive to make than making a hydrocarbon from CO2. Having to scrub the 0.03% CO2 out of the atmosphere, like plants do, doesn't sound like a feasible solution compared to recycling liquid CO2, unless you can prove me wrong on this. Liquid CO2 is much easier to deal with than either supercompressed hydrogen or liquid hydrogen. We could attack the energy storage problem on the recycling side, and stay with the current hydrocarbon/air systems as energy carriers. We're just not used to carbon sequestration and CO2 recycling from inside an engine, especially while mined hydrocarbons are so cheap, and emitting CO2 is so cheap. Liquid hydrocarbons(diesel, gasoline) are easily pumped, and relatively easily stored as government crude oil reserves, they occupy the sweet spot in the energy density diagram both in terms of weight and volume though for renewable energy storage the whole current engine technology would have to change. Hybrid-like electric cars would have to replace their conventional gasoline engine with direct methanol/ethanol/hydrocarbon based fuel cells, that emit the water but capture the liquid CO2 into a separate compartment, maybe even the same gasoline tank as a separate liquid phase, and then at a gas station the liquid CO2 would get unloaded at the same time that the hydrocarbon/methanol is loaded. This would be an absolutely zero carbon emission vehicle, with an easily recyclable oxide (carbon dioxide) to windmills, power stations. Imagine a steel cylinder of liquid CO2 next to each windmill, and a device that generates hydrocarbons from the CO2 + H2O +electricity. On your weekly harvesting tours you could tap the supernatant or undernatant hydrocarbon honey from these cylinders, and while refilling them with fresh CO2. Liquid carbon dioxide is just so nice to work with, so much easier to deal with than liquid hydrogen, because it stores at relatively low pressure at room temperature, and it's better than the similarly liquefiable liquid ammonia, because that's expensive to make, and it's toxic, and has an odor problem. The worst imaginable accidents with liquid CO2 would have zero environmental impact, other than the freezing/suffocation of nearby people. Gasoline, ammonia, liquid hydrogen, compressed hydrogen, methane are all more dangerous, while magnesium/aluminum is the safest, but can get dangerous if it catches fire. The CO2 losses due to accidents and leaks that are low energy waste so a not a big deal, can be made up by life-based carbon sources, but currently all life on the planet functions at about 70-100 TW compared to humanity's 15TW need, so a fully biodiesel/ethanol based economy is not feasible, we have to find a direct way to get to the solar energy, via windmills/solar stations, and then store this energy into something. If you only have to "make up" for CO2 losses, say a 0.1TW-0.5TW compared to a global 60TW consumption in 50 years, that's very possible to do life-based. The tools and methods in organic chemistry are so vast, that I have no fears that low temperature carbon dioxide reduction to fat-like hydrocarbons is possible, if nothing else, we know it's possible because life is doing it at 37°C. And life also figured out a way to combust the hydrocarbons at low temperatures with sophisticated catalysts - perhaps a non-fuel cell low temperature hydrocarbon-air battery is possible, something that Tesla used to dream about, that would give much better than 30% energy converstion currently in gasoline engines, or even 50% as in fuel cells. We can't make such sophisticated catalysts and enzymes, but as a starting point, superacids protonate and dissolve even candlewax, put it into a highly reactive state, and you can go from there. And we don't necessarily need the energy density of fat, simply non-bio CO2 derived ethanol, or methanol might suffice. It should be relatively easy to make methanol out of CO2. So so much for using hydrogen or aluminum as a hydrogen storage medium, or a metal air battery, we've been through this so much, and we're still back to hydrocarbons. If you can figure out an efficient way to extract in a concentrated form and recycle aluminum/magnesium/lithium oxides, while maintaining the high energy efficiency, and energy density, you might beat compressed hydrogen and liquid CO2-recycling based hydrocarbons. Just how high a concentration of aluminum hydroxide sludge are you making with your gallium or mercury based aluminum digestion, and how do you plan to recycle it, how pumpable is it, compared to liquid CO2? Pumping a liquid is just so much less work than having to haul it around on skids with a lift truck, I know it from first hand experience. One of the reasons that most steam engines were replaced by Diesel engines is that the train engineer doesn't have to shovel the coal anymore (besides having to carry lots of water, which drops the energy density/increases engine cost). Imagine having a Lexus where you have to toss some coal onto the fire while driving, or have a hopper high up in the air that gets stuck periodically from the caking aluminum/magnesium powder, or even a screw that pumps powder from under the car where the gas tank is, and malfuctions. Even most solids today, such as coal and rocksalt are handled like fluids on large scale, while mere mortals like you and I handle these things with a shovel, on small scale. It's a big deal. Dealing with liquids instead of solids is almost an absolute must anymore, as long as those liquids are not gaseous, or too light to store in any meaningful way. Liquid hydrocarbons are in such a sweet spot in all these respects when it comes to storing chemical energy, in their energy density by volume, by weight, being liquid fuel, and gaseous effluent, and most importantly, being able to store them as government energy reserves. In my opinion they are also by far the most ergonomic ways of storing hydrogen, compared to any other means of storing hydrogen. We may have to stick to them, just simply modify the gaseous effluent part, where the carbon emission is concerned, and recycle the carbon oxide. All other means of chemical energy storage have this issue of oxide recycling anyway - except hydrogen and liquid ammonia which have their own special issues - and carbon oxides are hard to beat with respect of ease of dealing with. By the way, coal as a solid fuel beats other solid fuels such as aluminum, magnesium, lithium, boron, lithium borohydride in ergonomics, by the fact that its combustion product is a fluid, not a solid, not a solution, even if this very fluid, CO2 gas, is the greenhouse gas that we're trying to stay away from emitting into the atmosphere. Silicon and aluminum oxides are ubiquitous, not very polluting. Still, can you picture cars going on a highway periodically ejecting chunks of aluminum or silicon oxides, basically clay and sand? What are the safety issues with such flying solids projectiles. Ejecting nothing as with batteries, or ejecting gases, or even liquids is so much better from the ergonomics, user friendly point of view. And by the way, we still use batteries even with gasoline/coal as the main energy carrier. Even if we don't get everything we want from aluminum/magnesium, there is still at least something to research. Namely, the organic electrolyte technology extended to aluminum and magnesium, similar to lithium ion, with conventional non-air anions (hexafluorophosphate or tetrafluoroborate) might drop the battery cost, at least as far as the price of aluminum/magnesium compared to lithium($40+/lb) goes, giving something intermediate in performance between lithium-ion and NiMH. Sillybilly (talk) 09:18, 30 March 2008 (UTC)
- Low temperature aqueous processes may never be economically competitive with molten salt processes, simply because of cell resistances/energy efficiencies. In that case it might be a good idea to have molten salt metal-air batteries next to pump storage stations, operating conventional electrolytic high temperature metal processing of magnesium (or aluminum), though they can't use chlorides, but need molten fluoride mixtures instead. When the pumped storage dam is full of water, drain half of it and make a magnesium mountain + pure oxygen, then when the levels stay low for a long period, shut the water flow, and consume the reserve metals in large scale metal-air batteries. This way you don't need to shuffle magnesium ingots around too much, and molten magnesium can be pumped as a liquid. This way you expand the grid capacity, make it more manageable, and renewables might be able to take up 100% of the grid supply because there is enough energy-room for longterm fat storage. Besides crude oil reserves, the gov't could update magnesium reserves, stored easily in big piles. For automotive/mobile applications, where you have to disconnect from the grid, current Li-ion batteries and compressed hydrogen should be able to replace gasoline engines, except people would have to get used to making more frequent pit stops, say every 50-100 miles instead of 150-300 today. That's not a big deal. Li-ion gets 95% efficiency in energy conversion, but hydrogen even with a fuel cell is way under 50%, while with a very simple internal combustion engine it's under 35%, but at least you can carry some decent energy density around with you, in an environmentally friendly way, because lithium ion is not very energy dense, due to the electrolyte/oxidizer. Still, metal/air batteries in a car would give well over 50% grid to wheel efficiency compared to hydrogen/air setups, with decent energy density compared to both hydrogen and li-ion. In a lithium-air system, one would pick up lithium metal at a gas station, and discharge lithium hydroxide. Lithium metal has a much better energy density per weight than either mg or aluminum, and the hydroxide is easier to reprocess, even via the low temperature organic/amalgam way, possibly using In/Ga/Bi/Sn expensive but nontoxic (compared to mercury) low melting alloys. Whether these alloys function at all has to be researched. For instance gallinstan with a -19C melting point wets skin, glass, etc., it's surface tension properties are radically different from mercury. On the other hand, while metal air batteries get a much higher grid to wheel efficiency than compressed hydrogen, the advantage of hydrogen is that the waste products can be vented to the atmosphere, while with metals the downside is that the oxides need to be carried back to the gas station. This is an issue with transportation because the weight increases as the vehicle proceeds on, instead of decreasing, so ultimately the vehicle gains the same weight as if the oxidizer were carried along in the first place. But this is not an issue for grid storage applications, such as pumped storage stations, where long term stable storage of renewable energy (solar, wind) (for up to 5-10 years even) in form of weatherable metal ingots/flakes is more important than the weight issue. Even a zinc/air or iron/air economy might make sense where weight is simply not an issue, because zinc and iron do have ok volumetric energy density, and their aqueous electrolytic processing is simple, no amalgams or organics needed, just high conductivity potassium hydroxide electrolyte with some additives, or an acid based electrolyte that's insensitive even to atmospheric CO2 absorbtion, even if lower conductivity, but easier to store in open air ponds, and water could simply be replenished as it's lost by evaporation. Iron can corrode if stacked, but zinc is resistant, and cheap, and easier to process in aqueous systems than aluminum, lithium or magnesium. The zinc ingots would be heavier and less energy dense mass-wise than any of those other metals, but still they might be the most economical next to a pump storage station, as a metal air battery, or as a renewable energy storage reserve. As long as the energy storage medium does not have to be carried for long distances, such as in an automobile, just locally moved around, as inside a plant environment, the density by mass may not be very important, as long as there is good density by volume, and ease of storage/handling. Pumped storage stations, or in general grid storage stations having to store compressed or liquid or even uncompressed hydrogen is a very expensive proposition, especially on a full year timeframe. So inasmuch as a hydrogen economy is concerned, hydrogen might be a useful temporary intermediate for transportation, but for longterm renewable storage, and grid energy storage one needs an magnesium/aluminum/lithium economy backbone, with government energy reserves vested in them, and a hydrogen economy only for short term transportation energy storage needs. In the 80's the japanese looking at batteries to store large amounts of energy concluded on a high temperature molten sodium/sulfur battery as most cost efficient. Unfortunately sodium and sulfur cannot be extracted from such batteries and stored easily as magnesium, aluminum + oxygen can from either high temperature molten salt/molten metal/oxygen batteries, or if the technology is found and is feasible, low temperature metal/organic/oxygen, or metal/organic/amalgam/aqueous/oxygen sources. (talk) 06:05, 29 March 2008 (UTC)
[edit] Greenhouse Gas
Proponents of a hydrogen economy suggest that hydrogen is an environmentally cleaner source of energy to end-users, particularly in transportation applications, without release of pollutants (such as particulate matter) or greenhouse gases at the point of end use.
Isn't water vapor a greenhouse gas?
69.20.226.218 (talk) —Preceding comment was added at 17:57, 5 May 2008 (UTC)
Yes, but there is so much liquid water on the planet's surface, that overall it is in an equilibrium, and only the global average temperature determines the amount of water vapor in the atmosphere, not how much you emit from vehicles. Extra water vapor above the overall equilibrium concentration precipitates out as rain, and if there isn't enough, more evaporates from lakes/oceans to get to the overall equilibrium saturation concentration. Basically you can't add more overall water vapor to the atmosphere by emitting more - it will simply precipitate out as rain. But you can add carbon dioxide and methane, which stay as gases. The only way to increase the overall water vapor concentration in the atmosphere is to increase the overall temperature of the atmosphere. In this sense water amplifies up the global warming effects: if anything causes a slight global warming, slight increase in the temperature, that will also increase the water vapor concentration too, therefore the temperature increase too. On the other hand, if a greenhouse gas concentration drops, so will the temperature slightly, so will the water concentration, and then the temperature even further. Water vapor on a global scale amplifies both the ups and downs. One note though, as the amount of water vapor increases in the atmosphere due to global warming, so might the amount of clouds, so more sunlight might get reflected back into outer space, causing global cooling, contrary to the expected global warming. Cloud formation and reflectivity also heavily depends on current pollution and fine dust/particulates in the atmosphere. The modeling and prediction of climate changes is very difficult. Sillybilly (talk) 16:09, 6 May 2008 (UTC)
[edit] More hydrogen in gasoline
The article says "there is actually more hydrogen in a liter of gasoline (116 grams) than there is in a liter of pure liquid hydrogen (71 grams)". A layman's reaction might be 'well, then why not use that?'. I assume this is bonded hydrogen, and it would be less confusing if that were explained. Actually, come to think of it, this is rather useless info. I bet there's more hydrogen in the car seats than in gaseous hydrogen, but how does it help to know something like that? It's just confusing, so shouldn't the sentence go? DirkvdM (talk) 07:25, 1 June 2008 (UTC)
