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One of the most important chemical reactions industrially - for better or for worse - is the production of styrene, which is of course, the chemical precursor for the widely used plastic polystyrene.

Humanity produces about 7 million tons of polystyrene per year.   It is widely used in a large number of consumer products, including, but not limited to, insulation for our wonderful modern sustainable energy efficient homes.   It is of course, also used in disposable coffee cups and stuff like that.

Polystyrene, because of its high level of chemical stability, actually represents a huge environmental problem, particularly in seawater, but it is not my point to cheer for polystyrene, but simply to make another point about the conversion of the most important energy waste form now facing humanity, carbon dioxide, into a commodity chemical.   Such use would serve to lower the propensity for simply dumping it into humanity's favorite waste dump, the planetary atmosphere.

The paper from the primary scientific literature I will discuss tonight is written by Chinese chemists and was published last year.   The reference is ChemSusChem 2011, 4, 341 – 345.   This journal is devoted to "sustainable chemistry."

The title of the paper is "V2O5/Ce0.6Zr0.4O2-Al2O3 as an Efficient Catalyst for the Oxidative Dehydrogenation of Ethylbenzene with Carbon Dioxide."


...some excerpts from the paper:

Vanadium has been widely used in catalysis because metal oxide- supported vanadia can catalyze many industrially important reactions, such as oxidation reactions.[1, 2] The activity of the supported vanadia is highly dependent on the specific oxide support[1–3] as a result of the so-called strong metal oxide–support effect. Although many researchers have attempted to gain insight into the catalytic mechanism, by using theoretic (sic) calculations and various characterization techniques, it is not yet fully understood.[4] Thus, the design of a high-performance supported vanadia catalyst, especially one with a high degree of stability, is still a challenge. The oxidative dehydrogenation of hydrocarbons (ODH) to alkenes is industrially important for various large-volume synthetic polymers. Because ODH with molecular oxygen as oxidant is a promising solution, many efforts have been reported.[ 5] Based on the concepts of dehydrogenation and selective catalytic oxidation of hydrogen, the commercial SMART process for the oxidative dehydrogenation of ethylbenzene was developed. This process co-feeds oxygen and steam in series reactor system.[5a, b] To overcome safety problems that result from mixing oxygen and light hydrocarbons, a novel idea to remove the dehydrogenation product of hydrogen by using reducible lattice oxygen was proposed,[5c–h] and a high-performance catalyst for the selective combustion of hydrogen in the presence of light hydrocarbons has been developed.[5e–h] Alternatively, ODH using CO2, being a soft oxidant without the problem of deep oxidation, is very attractive because it may open up new directions for oxidation reactions,[6] and create a new route for ODH.
Putting oxygen into a reactor with a hot organic molecule is, um, a little dangerous, as they point out.

Anyway, their new catalyst reportedly works quite well to substitute carbon dioxide for oxygen in this reaction, a much safer deal.

The reaction proceeds at 550C and the carbon dioxide is reduced to carbon monoxide, which is, of course, a useful synthetic intermediate for zillions of purposes.  It can, for instance, be used to make motor fuels.   The other side product is water.

Suppose that all of the styrene produced on earth were produced by this reaction.   It can be shown that since 7 million tons of styrene are produced each year, the use of this reaction would require about 2 million tons of carbon dioxide each year.

For a sense of scale, humanity currently dumps about 30 billion tons of carbon dioxide per year in its favorite waste dump, Earth's atomosphere.

But this is just one application for the utilization of carbon dioxide as a commodity chemical intermediate.

Recently, as I've reported elsewhere, the great chemist George Olah has written of the need for a closed industrial carbon cycle.   (The obvious input required is energy.)

Anthropogenic Chemical Carbon Cycle for a Sustainable Future.

This is the kind of approach that would be involved.

The reaction is actually much safer than the type of chemistry that is widely used for this sort of thing right now.

It's esoteric, but it's also kind of cool.

Have a nice day tomorrow.

Originally posted to NNadir on Sat May 05, 2012 at 09:30 PM PDT.

Also republished by SciTech.


Does this make you feel better about styrofoam?

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Comment Preferences

  •  The fact that China controls the world supply... (7+ / 0-)

    of cerium and thus can control our ability to make cheap plastic stuff with carbon dioxide, the fact that the ultimate starting material for styrene is benzene, little plastic balls all over the ocean getting into fish and everything else, the extreme photostability of polystyrene, the hidden consequences of polystyrene accumulating everywhere, other hide rates, and pure closed cycle recyclable troll rates all go here.

  •  Interesting stuff (1+ / 0-)
    Recommended by:

    I immediately guessed liquid fuels as you pointed out, can I assume nat gas too?

    Anytime one can push carbon and hydrogen around, one risks becoming a hydrocarbon.

    The potential of taking carbon out of the atmosphere to be stock in a liquid fuel, I would think, is way better than taking hydrocarbon crude oil out of the ground and burning it.

    Cool stuff, thanks.

    FDR 9-23-33, "If we cannot do this one way, we will do it another way. But do it we will.

    by Roger Fox on Sat May 05, 2012 at 10:33:03 PM PDT

  •  Chemical Engineering, on MY Daily Kos? (5+ / 0-)

    Next thing you know Obama will show up talking about the Reynolds number.

  •  The 40-ft. star of Dino De Laurentiis' ape epic (0+ / 0-)

    is alive and well.

    The ape whose death was staged at Manhattan's World Trade Center for the film's final scene was a Styrofoam stand-in.

    From: The King Leaks

    " 'In this world, Elwood, you must be oh so smart or oh so pleasant.' Well, for years I was smart. I recommend pleasant. You may quote me." Elwood P. Dowd

    by paulbkk on Sun May 06, 2012 at 02:13:44 AM PDT

  •  And your point is......? (0+ / 0-)

    WRT to CO2 pollution it is as you point out totally insignificant.

  •  Personally, I don't appreciate the (1+ / 0-)
    Recommended by:

    pimping of subscriptions to scientific journals.  We have all paid for the education of the scientific community, paying extra for their product (and I do consider that a valid product, unlike checking accounts) is unacceptable. The effort to sequester information behind the wall of currency is unacceptable to me.  Again, it's personal.

    That said, I am also not convinced that the etiology of oil as fossilized plant material is correct.  Natural gasses are being produced underground by anaerobic bacteria all the time. Fracturing the earth's crust to extract what is being produced in our dumps all the time because the destruction isn't visible is stupid.  I can see that getting rid of hazardous wastes via pumping at the same time seem attractive, but man-made toxins are dangerous wherever we put them because the natural systems are prepared to deal with them.

    People to Wall Street: "LET OUR MONEY GO"

    by hannah on Sun May 06, 2012 at 04:01:47 AM PDT

  •  And yet carbon sequestration is "evil" (0+ / 0-)

    Perplexing.  Hmmm.  Using fossil fuel produced CO2 in the industrial stream to make plastic crap that won't degrade but fills up landfills or enters the oceans to form microscopic particles that enter the food chain is good.

    But pumping fossil fuel produced CO2 into depleted natural gas wells is teh evul.

    Things that make you go hmmmmmm.

    •  No it's just stupid. (4+ / 0-)

      I believe you recently informed us that you know science because you work in finance.  

      Let's see, I think I can find that insipid comment easily, since it was the last grousing dumb Greenpeacy comment that you made in one of my diaries.

      Here it is:

      I know the science (2+ / 0-)
      Recommended by:Joieau, native
      I used to work in finance including project finance for power plants.

      Nnadir has almost no grasp of logic.  

      The diary is basically about how great nuclear power is because province destroying accidents create wildlife refuges.

      Uh, you know, you can create wildlife refuges without nuclear accidents.

      Namibia, which is preparing to build one of the largest solar power installations in the world as well as a nuclear power plant, has vast uncontaminated game reserves.

      Nnadir simply doesn't make any sense.

      And, btw, your HR is HR abuse.

      by HamdenRice on Sun Apr 29, 2012 at 12:25:09 PM EDT

      [ Parent | Reply to This ]

      That's a classic.

      Dumb guy explains his "science" education.

      Actually most people who do know science are aware of how clueless about the subject most financial types actually are.

      One of the functional idiots who showed up in that diaries commentary is a very, very, very, very badly educated anti-nuke who showed up and gave us a list of the half-lives of radioisotopes, not one of which had the correct value.

      The circle jerk of anti-nuke ignorance.

      She apparently cannot differentiate between a billion and a million.    Par for the course.

      There is not ONE anti-nuke who knows a shred of science, and you are certainly not an exception.    You have never made a scientifically literate comment in a single one of your heckling posts, because like the rest of the fools in "Nuclear Free DKos" your knowledge of science is nothing more than a fantasy.

      You see the second paper referenced in this diary, which by the way you are incompetent to read?    That's by George Olah.   He is a Nobel Laureate.   He's in his 80's and he is still working - purely out of a sense of decency - to save the world from stupid people who hate sciences they know nothing about.

      As I mentioned in your last heckle, I don't really believe anything anti-nukes say about their careers.    Given your level, I very much doubt you have ever been in a position of any responsibility of importance.

      Have a nice day.

      •  Illogical, non-responsive, as usual (1+ / 0-)
        Recommended by:

        So despite the baseless insults, why again is using CO2 to manufacture plastic a good thing, but sequestration a bad thing?

        Let's see if you can stay on topic!

        This is a quiz.  You will be graded on cognition and capacity to take instructions.

        Get ready, set, go!

        Btw, this is a timed quiz!

        •  Totally mature (2+ / 0-)
          Recommended by:
          NNadir, arroganceisstrength

          as always.

          Keep up the good work!

          •  No doubt about it. (2+ / 0-)
            Recommended by:
            bryfry, arroganceisstrength

            They guy's a real classic anti-nuke, the perfect companion to our friend Joy, so illiterate that he actually believes he's a genius.

            •  Uh oh, for you! (0+ / 0-)

              Looks like you're not part of the reality based mainstream of the DailyKos!


              Solar subsidies follow path well known to oil, gas, coal and nuclear industries

              by Meteor Blades for Daily Kos

              When the solar manufacturer Solyndra went bankrupt, the critics had a field day with the Obama administration because of its $500 million loan guarantee to the company. It wasn't just evidence of favoritism and corruption that the likes of Republican Rep. Darrell Issa went after. It was the whole idea of subsidies to clean-and-green energy in and of themselves.

              Much of the criticism was hoary ideological claptrap: the government shouldn't be picking winners and losers; there ought to be a level playing field among all energy sources; solar can never supply more than a teensy fraction of our energy needs; the renewables industry has gotten subsidies no other industry received. Ad nauseam.

              •  Oh no! (1+ / 0-)
                Recommended by:

                One person—who somehow bizarrely constitutes the "mainstream"—published a diary!!

                Wow! You really told him a thing or two! Keep up the good work!

                Now, please get back to us once you're done with puberty.

                •  He's the editor in chief of DailyKos (0+ / 0-)

                  That makes him pretty mainstream around here.

                  Or are you so ignorant that you didn't know who the editor in chief was of the website on which your profile states your main goal is to be quote an "asshole"?

                  If you spent a little more time focusing on what this site is about and less on being an "asshole" then you'd know who the editor in chief of the site is.

                  •  I know who he is (1+ / 0-)
                    Recommended by:

                    and I know that Timothy Lang is not the "Editor in Chief."

                    Once again, your uncanny ability to combine ignorance, inaccuracy, and breathtaking arrogance into one big mess of nonsense has not failed you.

                    If you had bothered to check the masthead, you would have seen that Timothy Lang, who writes under the nom de plume MeteorBlades, is a staff writer, who holds the specific position described as "Senior Policy Editor." His diaries express the opinion of one staff writer. That's all.

        •  because sequestration is stupid (1+ / 0-)
          Recommended by:

          not evil, just stupid.  It's like trying to load-balance your wind turbines by building a giant lead-acid battery, it's too expensive to matter.

        •  sequestration incidentially (0+ / 0-)

          is the exact same process used for disposal of wastefluid from fracking wells and other processes.

          I'm struck by how the meanest, cruelest, nastiest people brag about how they live in a Christian nation. It's rather telling.

          by terrypinder on Mon May 07, 2012 at 09:50:16 AM PDT

          [ Parent ]

  •  This is interesting, but unfortunately (4+ / 0-)

    probably not relevant from a carbon-capture standpoint even considering the huge difference between the amount of CO2 that would be used to manufacture the world production of styrene and the amount of CO2 we release.  Most CO2 used industrially is generated in the course of making ammonia or hydrogen from water and natural gas.  there CO2 sold that is released during the fermentation of corn to industrial ethanol but that is "food grade" and commands a higher price in those applications.

    There is some similar work I am aware of that may also be of interest - take a look here -the (nontechnical) article is on p 22 - and the associated additional web pages.

    I am not actually convinced that the process will scale efficiently or be cost-effective (and at any rate would need to be built out on unrealistically short timescales to affect our future climate) but it is at any rate an intriguing approach.

    •  I fully credit what you say about scaling and (5+ / 0-)

      other issues.

      That said, the use of carbon dioxide as an oxidant is I think a wise choice.

      I also like its use as a solvent:  Supercritical CO2 is getting a lot of attention these days, and that I think is a very good thing.

      Probably the best use of CO2 would be its use to phase out oil.   I personally think that the phase out of oil is technically quite possible, and Olah's arguments in this regard are compelling.

      I recall reading an interview with him where he was extremely frustrated because to him it was all so obvious.

      I recently had a brief conversation with a venture capitalist type who was giving a lecture on a swell (if somewhat glib) solar bio-oil scheme.   (I may write a diary about it sometime.)   His basic schtick was that we need to make "oil like" chemicals because that's what people buy.

      (The guy, à la Amory Lovins has been declared by some media types to be a "genius.")

      I found this conservative claim to be less than compelling.   I think that whatever chance humanity may have for surviving would more likely be involved in Olah's approach.

      He has been a big proponent of small simple molecules as energy carriers.    DME in particular is such a superior fuel that it seems incredibly foolish that humanity has not embraced on an emergency basis.

    •  By the way, I looked at your link. (1+ / 0-)
      Recommended by:

      I hadn't done so when writing the last post.

      Yes, that's the general idea.   The graphic is very much like the one in Olah's JACS paper.

    •  the convenience and functionality (4+ / 0-)

      of organic liquids and gasses as an energy storage and distribution mechanism is so established, and so obvious, that it's hard (for me, anyway) to understand the objection to continuing their use.  What has to stop is the mining of those materials, and the continued polution of the atmosphere with their combustion byproducts . . . issues both easily resolved if atmospheric CO2 plus a clean energy source is substituted for the mined Carbon.

      Small sale or large, anything that captures and re-uses industrial by-product CO2 is a positive step, and anything that captures and re-uses atmospheric CO2 is as well.  We are a LONG way from undoing a Century of uncontrolled burning, but there is, at least from a "technical" viewpoint, no reason for it to continue unabated (as it is, and will, absent determined and intelligent effort to stop it).

      Fake Left, Drive Right . . . not my idea of a Democrat . . .

      by Deward Hastings on Sun May 06, 2012 at 10:58:15 AM PDT

      [ Parent ]

      •  well, i don't know about that (0+ / 0-)

        gasoline is certainly a pretty good fuel, but ammonia would work just as well, and can easily be produced with a good source of heat and electricity.

        •  Ammonia Fuel (2+ / 0-)
          Recommended by:
          arroganceisstrength, PeterHug

          sounds good in a lot of ways, but I have one major reservation.

          Humanity's use of nitrogen fertilizer already causes environmental problems such as eutrophication of water bodies & the N2O produced in the course of denitrification is both a greenhouse gas & an ozone depleter. I would expect every spill & leak of ammonia fuel to add to this problem.

          OTOH the websites promoting ammonia as a fuel claim that ammonia fueled combution engines put out less NOx than hydrocarbon fueled engines. This should at least partially compensate for the effects of fuel leaks.

          Is anyone aware of a study of this issue? FAIK the ammonia fuel leak problem might be small enough that ammonia turns out to be the best (or least bad) solution.

    •  agree (1+ / 0-)
      Recommended by:

      burning coal and oil and natgas produces far more CO₂ than is needed for industrial applications.  Additionally, power plants where it's easiest to capture waste CO₂ for other uses are also the easiest to convert to using different sources of heat.

  •  Could Formosa (2+ / 0-)
    Recommended by:
    NNadir, arroganceisstrength

    Plastics' huge works south of Houston or a similar facility be required to retool and utilize its own "waste" CO2 and this cited catalyst to manufacture styrene and related byproducts,   as "Best Available Control Technology" for reducing its CO2 emissions, to replace its current production methods that emit CO2?

    •  Well, in theory yes, however, as another poster (1+ / 0-)
      Recommended by:

      noted here, it's not immediately clear that this would scale, or what the IP situation is.

      China is generally supposed to be involved in WTO and if so, we need to respect their IP if we can hope for them to respect ours.

      There is generally - but not always - some difficulty associated with moving something from the bench to industrial use.

      However I would love to see something like this go commercial.

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