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Sun Jul 31, 2016, 08:35 PM

Industrial Engineering and Chemistry Research devotes an issue to carbon dioxide capture.

The data this week at Mauna Loa comparing it to the same week of last year - 2015 was the worst year ever recorded for increases in the concentration of the dangerous fossil fuel waste carbon dioxide in the planetary atmosphere - is in:

On July 24, 2016, carbon dioxide concentrations rose 3.40 ppm compared to the same week of the previous year.

Among the 2113 such data points recorded since 1975, 3.40 ppm is worse than 97% of those recorded, but in 2016 it is rather unremarkable; in 2016 nine data points recording the increases in the dangerous fossil fuel waste carbon dioxide have exceeded 4.00 ppm over 2015, including the point on June 12 of this year which was the worst ever recorded, 4.78 ppm:

All time record set for week-to-week annual measurements of annual CO2 increases at Mauna Loa.

Eighteen of the 27 data points recorded this year have been higher than 3.40 ppm.

All of humanity's efforts to address climate change have been absurdly ineffective and have failed. I have not been restrained in noting that the most absurd of these failures has been the continuing faith based reactionary approach on relying on so called "renewable energy," which was, after all, abandoned at the beginning of the 19th century, and has undeserved and uncritical popularity in the early 21st century. It has resulted in the acceleration and not the arresting of dangerous fossil fuel waste increases. Many, if not all, of the advocates of this failed approach to addressing climate change object only in passing to dangerous fossil fuel use but instead choose to attack the world's largest, by far, source of climate change gas free energy, nuclear energy.

It does seem politically this dangerous faith in so called "renewable energy" at the expense of nuclear energy is unlikely to be arrested in the near term, and thus it will fall to future generations, whose interests are of no interest to our generation to try to restore whatever can be restored of this planet.

This will involve the capture of carbon dioxide from the air. This is an unbelievably complex and challenging thermodynamic, and thus engineering, problem. A scientific publication on the subject to which I have obliquely referred in various blog posts around the internet, had a rather discouraged view of the feasibility of doing this with current technology: Economic and energetic analysis of capturing CO2 from ambient air. (Kurt Zenz House et al Proceedings of the National Academy of Sciences,vol. 108 no. 51 > pp. 2042820433) Since it's publication in 2011 it has been cited 133 times; I picked up a few recent citations today to read to see if there are any new ideas; I suspect there aren't.

My hostility to so called "renewable energy" notwithstanding, it is pretty clear to me that the only possible means of capturing carbon dioxide will necessarily involve biological systems. This is not an endorsement of say, ethanol, or even the slightly better biofuel biodiesel, but is a suggestion that because biological systems are self replicating, and can cover huge surface areas using, um, solar energy, they are the only system that is capable of capturing carbon dioxide from the air. At high temperatures, biomass can be decomposed to mixtures of hydrogen and carbon oxides that are suitable, in the golden age of chemistry, to making pretty much any industrial chemical, as well as things like asphaltenes, carbon fibers, metal carbides and other refractories like silicon carbide, as well as graphene, graphene oxides and other functionalized graphenes.

To take full advantage of these capabilities, it will be necessary to separate carbon dioxide from gas streams with hydrogen, lower carbon oxides, and other chemicals in biomass. Although carbon capture has been generally investigated in the quixotic attempt to secure and sequester dangerous fossil fuel waste, the technology will actually be far more useful to any survivors in future generations in the role of planetary restoration, to the extent it will prove possible. The carbon dioxide could be captured (and utilized in ways that permanently fix it) during the reformation of biomass.

I alluded to how this might work elswhere: Better Chemistry, Better Biofuels? The Glycerol Glut, Solketal, and Other Floating Ideas

This is why I was very pleased to see during my weekly reading of one of my favorite journals, Industrial & Engineering Chemistry Research that the current issue is largely focused on reporting carbon dioxide capture strategies which were discussed at the recent International Conference on Carbon Dioxide Utilization. The issue is here: Industrial & Engineering Chemistry Research, Vol 55, Issue 29

If you have access, it's worth checking out some of the papers.

I can't help but to point to one paper that would be amusing were it not so frightening, this one:

Life Cycle Assessment of the Nitrogen Fixation Process Assisted by Plasma Technology and Incorporating Renewable Energy. (Ind. Eng. Chem. Res. 2016, 55, 8141−8153) This is a discussion of the predecessor to the Haber nitrogen fixation process - on which, by the way, the world food supply now depends - the plasma spark process which was abandoned in the early 20th century in favor of the Haber Process, because, um, the Haber process, um, works. The authors, showing that some scientists are not completely immune from buying into the failed and unsustainable so called "renewable energy" scam, "evaluate" the LCA, or life cycle analysis of plasma nitrogen fixation using vaguely defined "renewable energy." Interestingly, and probably more honestly than most of these "renewable energy" fantasies, the term solar is followed by the term "natural gas" frequently as in the following text from the paper:

Base Case Scenario. The base case scenario, as described above, is based on the assumption of 6% NO yield and a power consumption of 7.7 kWh/kg NO. For these conditions, the GWP of the plasma-assisted nitric acid production incorporating solar and natural gas energy sources, as a mean of electricity provision to the equipment presented in Table 4, is depicted and compared against the corresponding profile of the conventional process in Figure 3.

The solar industry is totally and completely dependent on access to the dangerous fossil fuel dangerous natural gas.

It is worth noting that industrial nitrogen fixation on this planet is responsible, depending on who you ask or what you read, responsible for about 1%-2% of world energy demand. World energy demand is now about 570 exajoules per year, meaning that nitrogen fixation, on which, again, the world food supply depends, consumes between 5 and 10 exajoules each year.

Solar energy and wind energy have never, not once, in half a century of wild cheering for them, ever produced in a single year 5 exajoules of energy combined.

Have a nice week.

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Reply Industrial Engineering and Chemistry Research devotes an issue to carbon dioxide capture. (Original post)
NNadir Jul 2016 OP
eppur_se_muova Jul 2016 #1
NNadir Aug 2016 #2

Response to NNadir (Original post)

Sun Jul 31, 2016, 10:33 PM

1. "because biological systems are self replicating, and can cover huge surface areas ..."

To borrow a line from an old CS joke, "... and can be mass-produced by largely unskilled labor". (The original reference was to the production of the uniquely capable, apparently massively parallel processor found in our skulls.)

This is the sort of argument that convinces me that biocapture is the best game in town for the foreseeable future, if one's aim is to remove, or at least abate release of, CO2. One has to be willing to consider the possibility that capturing CO2 without producing a lot of fuel -- maybe none -- may be a positive thing. This would certainly be the case if we attempted to recover land which has been denuded by one extractive practice or another, such as strip mining, slash-and-burn agriculture, deforestation for pasturage, etc. Let wild plants grow wild, stripping away roads and trails if that's what it takes, without any "payoff" other than restoration of ecological balance and recovery of topsoil. Of course, there's no $$$, and precious few votes, in that, and unless population control comes first, it's unlikely to happen. Just stopping some of the stupid stuff we're doing would be progress in itself, without any alternative energy sources.

And now for something completely different -- I did a very quick and superficial search for tributyrin, which can be made from glycerol and butanoic acid, a by-product of the fermentation of starch to 1-butanol. Couldn't tell if anyone has ever considered the fuel value of that (though it was tested as an oxygenated fuel additive for diesel fuel), but maybe that could serve as a sink for glycerol. Note that increasing production of butanoate by fermentation involves decreasing production of butanol, while increasing production of H2, which can be profitably diverted to other uses.

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Response to eppur_se_muova (Reply #1)

Mon Aug 1, 2016, 12:00 AM

2. Tributyrin and other esters of glycerol have been considered as oxygenated...

...fuels; one of the links to a post of mine elsewhere in the OP gives a discussion of another fuel oxygenate derived from glycerol, soketal, and even describes a completely biological route to it.

Soketal is the ketal of acetone derived from glycerol.

Of more interest in terms of carbon capture and sequestration is the conversion of glycerol into acrolein, a highly carcinogenic compound, but nonetheless, and important industrial synthon.

A recent paper in the same journal I referenced in the OP discusses the glycerol to acrolein route:

Hierarchical ZSM-5 Zeolite Synthesized by an Ultrasound-Assisted Method as a Long-Life Catalyst for Dehydration of Glycerol to Acrolein

Acrolein is a potential precursor to both propylene, used in the synthesis of polypropylene polymers, and methacrylate, used in the synthesis of acrylic polymers.

Thus used, these chemicals represent a form of fixed permanently sequestered carbon, although, of course, plastics are a huge environmental problem on their own.

I am not, however, a big fan of high value added isolation of pure biologically sourced molecules except in esoteric cases. The economic concern is that while glycerol is currently experiencing glut conditions and can be had basically for free, transport costs and the seasonal availability limit the economics. Currently polymers are made pretty much under continuous processes, not batch processes.

I'm not sure that enough biomass will survive the rapid climate change we are now sure to experience, especially given the ongoing disaster of the 2010's. It may be that the most available sources of biomass will be massive outbreaks of problematic seaweeds such as those recently observed in Florida or the very unfortunate oubreak of microcystin containing algae in Lake Erie last year.

This is poor pickings, but it may be all future generations will have. I suspect that future generations will be required to turn to the oceans, assuming they survive in some viable form, since, for just one example, much of the terrestrial phosphorous will have been depleted.

What will be required for the collection of this biomass, and for its use as feed for hydrothermal reformation to hydrogen and carbon oxides will be greenhouse gas free pumps and/or ships. Only nuclear powered pumps and nuclear powered ships can do this job with high carbon capture efficiency, and thus, the technology will require a different culture than the unfortunate one in which we live. This will fall to the future generations we have screwed beyond any semblance of ethical restraints, and they will have fewer resources, and be much more impoverished than we are, if they exist at all as a result of our blank stupidity.

We have proved to be criminally insane in our approach to the future, and one hopes enough knowledge will remain after us that they, the survivors of our stupidity, may have some hope of restoring the planet. It's a long shot now, and my general view of the future in which my own sons will live is increasingly dystopian, but I can hope I'm wrong.

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