Aluminum formate Al(HCOO)3: Earth-abundant, scalable, & material for CO2 capture

https://www.science.org/doi/10.1126/sciadv.ade1473

by westurner • 4 years ago

122 99 4 years ago

westurner2• 4 years ago

"Aluminum formate, Al(HCOO)3: An earth-abundant, scalable, and highly selective material for CO2 capture" (2022) https://www.science.org/doi/10.1126/sciadv.ade1473

Abstract: A combination of gas adsorption and gas breakthrough measurements show that the metal-organic framework, Al(HCOO)3 (ALF), which can be made inexpensively from commodity chemicals, exhibits excellent CO2 adsorption capacities and outstanding CO2/N2 selectivity that enable it to remove CO2 from dried CO2-containing gas streams at elevated temperatures (323 kelvin). Notably, ALF is scalable, readily pelletized, stable to SO2 and NO, and simple to regenerate. Density functional theory calculations and in situ neutron diffraction studies reveal that the preferential adsorption of CO2 is a size-selective separation that depends on the subtle difference between the kinetic diameters of CO2 and N2. The findings are supported by additional measurements, including Fourier transform infrared spectroscopy, thermogravimetric analysis, and variable temperature powder and single-crystal x-ray diffraction.

westurner2• 4 years ago

"NIST Breakthrough: Simple Material Could Scrub Carbon Dioxide From Power Plant Smokestacks" (2022) https://scitechdaily.com/nist-breakthrough-simple-material-c... :

[What to do with all of the captured CO2?]
> - Generate more formic acid to capture more CO2

- Make protein powder (#Solein,). And nutrients and flavors?

- Feed algae

- Feed plants, greenhouses

- CAES Compressed Air Energy Storage

- Firefighting: https://twitter.com/westurner/status/1572664456210948104

- Make aerogels. Aerogels are useful for firefighter protective clothing, extremely lightweight insulation, extremely lightweight packing materials, aerospace; and no longer require supercritical drying to produce: https://twitter.com/westurner/status/1572662622423584770?t=A...

- Make hydrogels. Hydrogels are useful for: firefighting: https://www.google.com/search?q=hydrogel+firefighting https://twitter.com/westurner/status/1572664456210948104

- Make diamonds, buckyballs, fullerenes, graphene

- Water filtration: activated carbon, nanoporous graphene

Is there a similar process ("MOF,) for capturing Methane from flue gas? Is that before or after the CO2 capture?

- Methane is worse for Earth than CO2 FWIU. And there are many uncapped wells leaking methane, as now visible from space: https://news.ycombinator.com/item?id=33431427

- It's possible to make CBG Cleaner Burning Gasoline from methane (natural gas)

How does the #CophenHill recycling and flue capture facility currently handle CO2 and Methane capture?

- "Transforming carbon dioxide into jet fuel using an organic combustion-synthesized Fe-Mn-K catalyst." (2020) https://doi.org/10.1038/s41467-020-20214-z https://news.ycombinator.com/item?id=25559414

lzazz• 4 years ago

When we have CO2 capture running, will all the money from "CO2 credits" that was stolen from businesses be returned? :')

rowanG077• 4 years ago

I'm not familiar with that but I assume it would actually be spend on things such as this

phtrivier• 4 years ago

Is this something to be used for CC at power plants ? Or does it have any application to DAC ?

cbracketdash• 4 years ago

Chemist here. Looks promising for CO2 scrubbing !

However, my instincts would keep me cautious around this chemical. The formate ion forms formic acid and eventually formaldehyde which is extremely toxic to humans. In addition, many organoaluminum compounds (i.e DIBAL) can cause serious damage (like blowing up labs... seriously). If a bunch of this stuff was in the atmosphere, it could be quite dangerous to human life.

Otherwise, I am quite interested to seeing how this could be implemented.

MgB2• 4 years ago

The compound presented here is, however, not an organoaluminum compound. Those have Al-C bonds and are indeed very reactive. Aluminum formate has the Al3+-ion coordinated only by oxygen, and will certainly not exhibit the reactivity you described.

brilee2• 4 years ago

Chemist here.

Formate does indeed act as a reducing agent under appropriate conditions, but its byproduct is typically CO2 gas, not formaldehyde (HCOO- -> CO2 + H+ + 2e-). Aldehydes are generally unstable with respect to disproproportionation and are therefore unlikely reaction products.

Organoaluminum compounds are molecules with direct Al-C bonds, whereas these are effectively normal ionic salts with some unusual unit cell structure. Conflating DiBAl with aluminum formate is akin to conflating chlorine gas with clhoride anion...

refurb• 4 years ago

Formate ions can disproportionate:

HCO2H -> CO2 + H2

HCO2H + H2 -> HCHO + H2O

However, aluminum salts of formate are likely more stable? You usually need formic acid and heat to generate hydrogen.

kragen10• 4 years ago

also if you get trace amounts of formaldehyde out the smokestack it isn't going to last more than a few hours in the environment. every living thing produces formaldehyde

jokoon• 4 years ago

Any physicist seems to say co2 is a neutral molecule which makes any carbon capture tech very energy intensive, whatever technology it uses.

Tired of money trying to greenwash lies.

usrusr2• 4 years ago

That's why the smart people focus on capture from flue gases, which might be generated not only from fossil fuels but also from renewable biomass (basically the same just so much younger) and leave aside the direct air capture follies. Guess which side the process described in this article is on.

midislack4• 4 years ago

CO2 is a great red herring, the real cancer toxins and forever chemicals are spewed more every year while people scramble to sequester a harmless substance. In the distance, Bayer-Monsanto is laughing at all the useful idiots.

sebstefan• 4 years ago

Climate change has nothing to do with cancer

midislack4• 4 years ago

Not so fast, persona!

https://cancerletter.com/guest-editorial/20220729_5/

mqus• 4 years ago

why not tackle both?

orangepurple• 4 years ago

Big CO2 counter propaganda has pushed the other stuff out of the limelight

BoGoToTo2• 4 years ago

I challenge you to find a single peer-reviewed paper that states excess CO2 is not a contributing factor for anthropomorphic climate change.

IngvarLynn• 4 years ago

I challenge you to discover Russel's teapot.

midislack4• 4 years ago

Didn’t you read the Climategate mails? Academics in charge of climate journals admitted to “changing the meaning of peer review.” I’m under no obligation to listen to these communist prognosticators after an admission like that.

rocqua5• 4 years ago

If I read this correctly, this is mostly aimed at the smoke-stacks of fossil fuel plants. Great for reducing their harm before we phase them out, and valuable especially if it is cheap enough to actually be plausible. Cheap here matter more than perfect, since the problem of emitting CO2 from fossil fuel plants is better (but more slowly) solved by phasing out fossil fuel.

But how does this work for scrubbing CO2 from general atmosphere, is it anywhere close to an option? Once we have 'solved' the problem of no longer emitting CO2, we will almost certainly still have way more CO2 in the atmosphere than we want. Does this new scrubber material make it feasible to reduce the CO2 from the atmosphere, or will it be more economical to deal with the symptoms of high CO2 levels?

microjim• 4 years ago

Trees

twawaaay4• 4 years ago

Trees do not reduce CO2 in long run.

For starters, humanity emits more CO2 than the combined mass of entire biosphere (every living organism, not just trees), every 10 years. Even if we were somehow able to cover all landmasses of Earth with trees (which we can't) and thus double/triple the biomass we would only set back the problem by a decade or two.

Second, trees are part of a cycle. They store the CO2 temporarily, then release it mostly back to the atmosphere -- very small part becomes soil.

Trees are not a magical solution that is somehow constantly sequestering CO2 from atmosphere. Trees store a bit of CO2 once and then it stops and can even easily be reversed (if you burn it down). New growth is necessary to keep the store at the same level, otherwise the trees will burn or die and CO2 is returned to the atmosphere.

elmolino899• 4 years ago

Does this new scrubber material make it feasible to reduce the CO2 from the atmosphere, or will it be more economical to deal with the symptoms of high CO2 levels?

The low tech solution for scrubbing C02 from the atmosphere is to get more plants absorbing it and prevent the plant decomposition back to CO2 or even worse to methane. Some of the agricultural waste may be just buried in the fields helping to build the organic matter in the soil, but it would be hard to avoid any CH4 emissions doing it. Just check any landfill with buried organic matter and some sipping in water. One can try to use pyrolysis and get charcoal. This would not be 100% emissions free (CO, CO2, CH4 etc.).

The main problem with the above is that collecting wood/straw/etc. transporting and then processing it also requires energy, at least on land. Converting the millions of agro machines to run on batteries or hydrogen would not be carbon neutral either.

Supposedly if we fertilize patches of the oceans the dead algae will nicely sink to the bottom not to be release CO2 for centuries.

imhoguy• 4 years ago

if we fertilize patches of the oceans

Don't we do it already with wastewater streaming down from fields, pipes, rivers...?

leoedin• 4 years ago

My favourite solution to this is to use some of the pyrolysis products as fuel - if you burn and release 20% of the carbon captured by the plants to power the process of burying the remaining 80% the process is still carbon negative overall, and you have a nice to use hydrocarbon fuel that can more-or-less slot into existing machinery.

The biggest problem is the scale of it - to make a significant dent in global co2 you need to be pyrolysing a lot of wood - getting towards entire-earth scale managed forests.

usrusr2• 4 years ago

Better yet: you burn the plants for energy, then sequester the conveniently high concentration CO2 from the smokestack and do with it whatever you'd think would be smart to do when burning fossiles.

About the Science article: my quick skim stumbled over the word "regenerate", which tells me it's not about some material suggested for permanently binding the carbon, but about a tool to get from smokestack-level CO2 concentrations to even higher levels?

formerkrogemp• 4 years ago

Supposedly if we fertilize patches of the oceans the dead algae will nicely sink to the bottom not to be release CO2 for centuries.

This is not true. Russ George is and perhaps always will be a grifter.

https://en.m.wikipedia.org/wiki/Iron_fertilization

mayama• 4 years ago

There isn't enough arable land and fresh water to meaningfully address climate change in the time necessary. Algae farming with sea water might be a good alternative if we could address disposing the the algae without emissions.

mschuster912• 4 years ago

The low tech solution for scrubbing C02 from the atmosphere is to get more plants absorbing it and prevent the plant decomposition back to CO2 or even worse to methane.

Bring back moors. Moors can sink a shitload of CO2 - and there have been a lot of moors de-watered over the last centuries to gather peat and agricultural land.

The downside is you have to convince or pay off a lot of farmers who have farmed the former moors for just about the same timeframe.

rocqua5• 4 years ago

Stupid idea of mine: can we start burying our paper rather than recyling it? It means every sheet of paper requires cutting down more trees, and hence putting more trees (indirectly) into the ground. If you then re-plant those trees you capture more carbon.

I presume the paper doesn't add enough to create soil and just rots.

dools• 4 years ago

Scrubbing C02 is important for industrial processes other than energy production so it’s very important to get it right otherwise we can’t fabricate stuff without increasing emissions and building renewable infrastructure while adding another 3.5b people to the population is going to involve a lot of fabrication.

twawaaay4• 4 years ago

Cheap here matter more than perfect, since the problem of emitting CO2 from fossil fuel plants is better (but more slowly) solved by phasing out fossil fuel.

The goal is to stop emitting CO2, not phasing out fossil fuels. If you can use fossil fuel without emitting CO2 (and other greenhouse gasses), then the goal is achieved.

But we also know that fossil fuels are finite and it might be worthwhile to stop using them and learn to use alternatives before we get forced to do it when the sources run dry.

For me the most tragic part of the current situation is that if we somehow destroyed our current civilisation, there would be no raw resources to support a new industrial age.

ethbr02• 4 years ago

If we somehow destroy our current civilization, then world population will plummet from starvation, especially in the third world that isn't fertilizer-self-sufficient.

And we'll still have plenty of raw coal + recyclable metals.

rocqua5• 4 years ago

I don't think there are (economical) ways to stop emitting CO2 without phasing out fossil fuels. And like you said, regardless of CO2, fossil fuels will run out anyway.

I wonder if any new civilization could bootstrap off existing knowledge and artifacts about electricity. Wind and water based electricity don't require stupidly complicated tech to get going. You can probably mine copper from ruins rather than mines. Similarly, perhaps current stores of coal and oil could also support some systems for long enough? Heck, I could even imagine old oil wells to be 'easy' to re-open.

In any case, neither I nor my children will be around after we destroy civilization. So I care much more about avoiding the destruction than the ability to rebuild afterwards.

brilee2• 4 years ago

Good question. I was also suspicious of the angle/framing of the paper as a smokestack capture solution. My thoughts are

1. smokestacks are a great place to start, it's thermodynamically easier, has low-hanging fruit, and can be a stepping stone to a atmospheric DAC solution.

2. I bet that the smokestack angle of the paper is due to ALF being a decent oxygen absorber. The paper made the argument that the CO2 (diameter 330pm) vs. N2 (diameter 364pm) selectivity was due to size exclusion principles. But oxygen has diameter 346pm, much closer to CO2, so it would stand to reason that oxygen would compete for CO2 binding efficiency. If you read the supplementary materials/experimental conditions, literally every experiment is done under a protective flow of 99.95% N2 gas, indicating that this compound is not to be exposed to air.

rocqua5• 4 years ago

Interesting angle.

Even if this only works in smokestacks, it is hugely valuable. We will be stuck with some fossil fuel in the coming few years at least. Making those years less polluting is worthwhile.

I suppose there is a risk that people say "we can do fossil fuel a bit longer, we scrub it now", but I think that will pretty soon be a clearly untenable position.

ars2• 4 years ago

aimed at the smoke-stacks of fossil fuel plants

"CO2 from dried CO2-containing gas streams"

The word "dried" is going to cause trouble. Smoke stocks have a lot of water - more water than CO2 actually.

angst_ridden• 4 years ago

Yeah, and in gas/oil-fired electric turbines you typically inject a whole lot of water to create more mass going through.

A power plant I worked at in the 90s tried to keep a 4:1 ratio of water to fuel oil.

It was always amusing to explain to lay-folk that we "burned more water than oil," even if it wasn't technically precise.

rocqua5• 4 years ago

The article states that the major advantage of this new material is much better resistance to water. Are you saying that the levels of water described in the paper are still way below untreated flue gasses?

Mizza12• 4 years ago

Always flue gas, never atmospheric concentrations.

We have loads of good ideas for scrubbing flue. We have no good ideas for atmospheric CO2.

420/1000000 isn't a lot of particles per million. Moving and concentrating those particles and grabbing them is going to require an _incredible amount of energy_ no matter how you swing it. People have not comprehended the scale of this challenge yet.

ealexhudson• 4 years ago

If the source of the flue gas is ~renewable (e.g. wood) and the energy generated is used usefully, this isn't a bad idea for carbon capture. It's much easier to capture the carbon technologically like this, and rely on broader capture (e.g. trees) to pull it out of the atmosphere. What really counts is what happens to the concentrated carbon being extracted - it needs to not go back into the atmosphere.

amelius• 4 years ago

How do trees do it, then?

bjornsing• 4 years ago

Sunshine. Lots of it.

pjc502• 4 years ago

At about 3% efficiency, but compensating by being spread over a large fraction of the land surface.

Mizza12• 4 years ago

One adult tree captures 25kg per year. One transatlantic flight releases 500kg per passenger. Twenty trees, per person, per flight. Get serious.

IPCC projections for a "good" scenario still depend on magical BECCS processes that don't yet exist., not flue scrubbing, which I think if anything will be away to keep coal plants online for _longer_.

It's still valuable science, but don't get excited until there are major, major advancements in non-flue DAC/CCS.

kragen10• 4 years ago

direct air capture has been demonstrated by a variety of methods, including the literally oldest human industrial chemical process, lime burning. i've done the calculations, it's not such a bfd, even with lime

yes, it requires an incredible amount of energy

guess what solar panels give you

Mizza12• 4 years ago

I would be very curious to see that math that you solved the problem with, given that all of the scientists in the world working on this missed your solution.

lemming• 4 years ago

We have no good ideas for atmospheric CO2

https://www.projectvesta.org is the best-looking option I have seen for this.

Mizza12• 4 years ago

The one I am most interested in is https://verdox.com/

namibj• 4 years ago

Yes we do, they don't work in all climates, but we do have a quite well-working approach:

Step 1: base-resistand swamp cooler structured packing. Step 2: NaOH or KOH solution in water, at equilibrium with air (temperature& humidity). Step 3: blow air sideways while running liquid down via gravity. Step 4: regenerate liquid via salt metathesis reaction on column packed with Ca(OH)2. Step 5: dry-distill the CO2 out of the CaCO3 in a lime kiln (carbon capture for those is easier than for a gas turbine, as they exhaust like around iirc 3~5x as much C02 for each oxygen you feed in, assuming you fuel both with the usual methane). Step 6: inject the captured CO2 into old gas/oil formations.

Of course this would be better if you combine it with already-needed air handling, for example in central forced air HVAC installations where adjusting the concentration of the lye in step 2 through adding water or vacuum-distilling allows it to humidify/dehumidify the air and where the liquid/air contact can also easily do the heat exchanger task (that strongly basic water shouldn't support growth of any harmful micrograms, I think (for KOH it would typically be half the molarity of a saturated solution, for NaOH more like 80~90%)).

They use similar scrubbing but in dry columns (Ca(OH)2 beads soaked with NaOH solution, then left to drip and packed into canisters) for anesthesia rebreathers to scrub a patient's exhaled CO2, and similar lime/lye cycling in paper Mills (Kraft process; green liquor (sodium carbonate + sodium sulfite) to white liquor (sodium hydroxide+ sodium sulfite) recausticizing).

Assuming negligible cost of the initial wet air scrubbing (via fusing the air handling with HVAC and in the process even providing extra-low-CO2 air), assuming a methane-fired lime kiln, this overall prices should be able to compensates for around 2~4x as much fossil fuel burn in, say, vehicles, than the burn/consumption of the DAC plant.

And much of the process is quite amenable to using solar electricity (with about a day's worth of storage, but part might be able to use thermal storage in rock piles for pre-heating the kiln gas feed), especially as nothing really requires the lime kiln to work in the winter.

muaytimbo• 4 years ago

One thing that is suspiciously absent from the abstract is the stability of this material to O2.

jonnycomputer• 4 years ago

I suspect that there are applications and industries that cannot fully be decarbonized. For example, steel production. So anything that can capture carbon from that (8% of global CO2 emissions, I believe) would be fantastic.

Aluminum formate Al(HCOO)3: Earth-abundant, scalable, & material for CO2 capture

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