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CO2 Conversion to Methanol

02/25/2016 3:46 PM

USC research was reported on the following link a while back:

http://insights.globalspec.com/article/2158/method-to-convert-co2-to-methanol?frmtrk=cr4digest&et_rid=614380648&et_mid=82898642

I think this has some merit. They report that the homogeneous Ruthenium catalyst is good for about six cycles of operation. Surely there is an easy way to restore the catalyst, or at least recover the Ruthenium (which is sort of expensive, as I recall). The reaction obviously requires 3 moles H2 per mole CO2, with methanol and water 1 mole each as products. What were they sourcing the H2 from?

There was no cost analysis in the article, and perhaps that is confidential, but it is too bad. All that was mentioned beyond this was the process temperature range and that it is too expensive to use this for methanol while oil is in the $30/bbl range.

Isn't that just a bit vague? Methanol is so useful in industry, and is usually made from petroleum through various processes. What are the potential heat sources to keep a material in the 125 to 150 °C range? Did they consider CSP, possibly using the coolant for PV cells as reaction heating medium? Then one could have more bang from his buck?

Any opinions how to economize this process (other than a massive scale-up = massive economic hemorrhage)?

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#1

Re: CO2 conversion to methanol

02/25/2016 3:54 PM
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#21
In reply to #1

Re: CO2 conversion to methanol

02/26/2016 8:42 AM

This research seems to be preliminary, and in need of refinement. I noticed this group also mentioned Ruthenium. I spent considerable time my senior year of college inorganic chemistry advanced topics synthesizing a novel Ruthenium compound, at least that was the target molecule. The result was a brown residue harder than hell to scrap off the evaporating dish, and apparently not pure based on liquid chromatography result (there were at least three bands. Ruthenium is related to iron in its position in the periodic table, but has completely different coordination compounds due to its 4d75s1 electronic structure. I think a combination of titanium and ruthenium or cobalt will be the best catalyst in the long run, maybe.

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#2

Re: CO2 conversion to methanol

02/25/2016 4:16 PM

Something about first sentence in the article bothers me a bit...

"Researchers at the University of Southern California's Loker Hydrocarbon Research Institute have developed a method for converting carbon dioxide (CO2) into methanol-a fuel for internal combustion engines and fuel cells and a raw material used to produce many petrochemical products."

Using it as a fuel, you just get the carbon dioxide back again with a net loss of energy.

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#3
In reply to #2

Re: CO2 conversion to methanol

02/25/2016 5:44 PM

Yes. Trees have been converting CO2 and water into methanol using sunlight for eons. And the trees' emissions have not yet been designated as a pollutant.

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#5
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Re: CO2 conversion to methanol

02/25/2016 7:09 PM

"And the trees' emissions have not yet been designated as a pollutant."

On your behalf the government is tirelessly working on solving that problem.

They may not be direct pollutant sources but when burned they can create smoke and heat that is bad for you which thusly should give them credence as potential sources of pollution which is enough for most government officials to put them on a list someplace.

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#7
In reply to #5

Re: CO2 conversion to methanol

02/25/2016 7:17 PM

This is the pot calling the kettle black, for sure!!!

Tire burner!!!!!!!!!!!!!!!!

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#8
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Re: CO2 conversion to methanol

02/25/2016 7:59 PM

Well I do occasionally use wood to get those tires burning so..........

I don't recall ever having claimed that I or anything I have ever done was benignly environmentally friendly either.

Nature puts as much effort into killing a Butterfly as it does a Wasp but one gets a way wider path to travel in life while it's alive. I like my wide path.

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#14
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Re: CO2 conversion to methanol

02/26/2016 12:46 AM

And also we must remember that the trees' emissions are a SIGNIFICANT component of a greenhouse gas.

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#16
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Re: CO2 conversion to methanol

02/26/2016 6:00 AM

I don't think so. The significant component of tree emissions, as far as life on earth is concerned, is oxygen.

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#22
In reply to #16

Re: CO2 conversion to methanol

02/26/2016 9:55 AM

Yes. O2.
CO2.
Behold, humor.

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#27
In reply to #16

Re: CO2 conversion to methanol

02/26/2016 12:51 PM

And water vapor too. The most prevalent green house gas there is.

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#6
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Re: CO2 conversion to methanol

02/25/2016 7:16 PM

and all this time I thought they made glucose

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#26
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Re: CO2 conversion to methanol

02/26/2016 12:48 PM

Especially good when one particular variety is boiled down and poured over a stack of pancakes.

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#9
In reply to #3

Re: CO2 conversion to methanol

02/25/2016 8:28 PM

Trees convert carbon dioxide and water into wood and require very little maintenance...

http://www.arborenvironmentalalliance.com/carbon-tree-facts.asp

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#37
In reply to #3

Re: CO2 conversion to methanol

03/03/2016 4:18 PM

Trees convert carbon dioxide into a building material, produce oxygen, and create copies of themselves, all without human intervention. How can it get any better than that?

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#38
In reply to #37

Re: CO2 conversion to methanol

03/04/2016 8:19 AM

So you want a car that burns wood, right?

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#39
In reply to #37

Re: CO2 conversion to methanol

03/04/2016 9:41 AM

Wood gas is one method of using trees for ICE fuel. It was used by many countries during WWII to keep non-military infrastructure moving. One could also go back to steam.

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#40
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Re: CO2 conversion to methanol

03/04/2016 10:55 AM

Southern Illinois University is making progress on a method to bacterially convert coal to methane for cleaner burning. There's probably a step missing, but wood to methane could be a possibility.

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#18
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Re: CO2 conversion to methanol

02/26/2016 8:30 AM

I think that would be the general idea...doh! I the idea is to produce methanol for use in gasoline blending (maybe) and as feed stock for biodiesel production. The overall scheme of "things" is to add some contribution of "carbon neutral" cycles to the overall fuel food chain. This would benefit food commodity markets by making more corn available once again as animal feed, and people food.

Of course, direct production of hydrocarbons is even better, as this fits right into existing fleet and infrastructure, and does not pollute when spilled the same way that methanol would, although we already safely produce and use vast tonnage of methanol.

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#4

Re: CO2 conversion to methanol

02/25/2016 5:50 PM

I much prefer Ethanol instead of Methanol.

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#10
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Re: CO2 conversion to methanol

02/25/2016 8:30 PM

But not made from oil!

original post:

... and is usually made from petroleum through various processes. ...

To make Ethanol the organic solution via plant material (hops and malt) is the preferred method!

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#11
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Re: CO2 conversion to methanol

02/25/2016 9:47 PM

But isn't petroleum made from plant material by a very long aging process.

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#12
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Re: CO2 conversion to methanol

02/25/2016 10:35 PM

Does that make it the ultimate single malt????

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#15
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Re: CO2 conversion to methanol

02/26/2016 1:35 AM

Maybe, maybe not.

The inorganic petroleum cooking idea is still out there.

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#17
In reply to #15

Re: CO2 conversion to methanol

02/26/2016 7:14 AM

The flat earth idea is also out there.

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#28
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Re: CO2 conversion to methanol

02/28/2016 10:43 PM

Haha!

So you say there is no truth in it? But I can live with the idea that there is bacteria down in 3000 m depth converting carbons into oil.

Common some places on Earth are flat. And I guess for gravitational waves the Earth is as flat as a pancake, its just us that think its a spherical body.

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#29
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Re: CO2 conversion to methanol

02/29/2016 11:27 AM

Really? Were there no bacteria when the algal mass sank to the bottom of the ocean?

I think the bacteria starts the digestion/degradation process long before the sediments even reach the bottom of the ocean. Also, most of the ancient carbonate seas (where very large algal blooms are known to take place) tended to be shallow, warm seas.

I hope that explains my position on the topic slightly better.

I am trying to remember the "recent" discovery of long-chain waxy materials originating from algal die-offs that were discovered off West Africa (these types of compounds actually have been used as a sort of clock in one sense). The interesting thing is these offer a fast, low temperature conversion to diesel by clipping the ketone groups in some really high molecular weight molecules from ancient algae. I just can't remember the term used to refer to them. Help, anyone?

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#20
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Re: CO2 conversion to methanol

02/26/2016 8:36 AM

The theory goes that certain algae have historically produced vast blooms in the ancient carbonate seas, and this led to large scale die offs of the algae (see algal growth curves) when the population reaches zenith (the top part of the S-shaped curve for those in Rio Linda). The biomass then sunk to the bottom (depends on certain oxygenates being present that add density (I think), and rotted, leading to oil and gas over time. There is already a way to speed this up to a matter of less than one minute using high heat.

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#30
In reply to #11

Re: CO2 conversion to methanol

02/29/2016 12:41 PM

"...isn't petroleum made from plant material by a very long aging process."

Of course , THAT is what people have had drilled-into-their-craniums for SO long now, it is (almost) universally believed... because that is what most people WANT to believe. "[MELLOWED A HUNDRED MILLION YEARS]"

I have a hard time DISMISSING certain evidences to the contrary. Innumerable things have been found, both (embedded) in coal AND while drilling for oil, that clearly indicate the "opposing view".

And given the fact that 'scientists' can replicate the process of "turkey guts to oil" in a matter of hours, a thinking person might answer:

"That's not necessarily true." ... (hmmm... from which movie am I recalling that as a quote... "Independence Day", perhaps...?)

"PS" - The same goes for petrification. I recall having been taught (er, more like "indoctrinated") that petrification takes hundreds-to-thousands of years. Yet, scores upon scores of items exist that have petrified in (by comparison) "no-time-at-all".

Cheers!

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#31
In reply to #30

Re: CO2 conversion to methanol

02/29/2016 1:47 PM

How do we know anything we were not around to observe? ONLY by extrapolating observable data to time before hand. This always assumed straight line behavior, (or log line behavior, or other depending on what little is known about natural processes). Some of these extrapolations work, but I will never forget the warning received in analytical chemistry class that one "never" extrapolates from the known calibrated range of analysis into the "unknown" zone where sensor behavior is not calibrated. This is not what I am talking about. Certain fundamental processes of physics and chemistry may well be extrapolated (within a range of possible temperatures, pressures, etc.).

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#34
In reply to #31

Re: CO2 conversion to methanol

02/29/2016 4:20 PM

? Re: "This is not what I am talking about."

My sincerest apologies, but, having read-&-re-read your post (in the context of a REPLY-TO my post #30): I am not sure that what you were meaning by what-all it is that you stated was what you really intended for me to understand from it, since I haven't yet figured-out what that was, or was not...

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#36
In reply to #34

Re: CO2 conversion to methanol

03/01/2016 9:18 AM

I agree that my post was not clear in intent. I was saying there are but a few instances where extrapolation of existing time dependent data into the past is allowed. One of which is the conversion of one allotrope to another, as long as the physical process and energetics are clearly understood. Another is radioactive decay of one isotope to another (C14 is one prime example, and well understood). Other dating methods rely upon daughter isotopes from uranium decay series, etc. This is considered to be hard science, based upon facts.

One may not extrapolate data where data outside the calibration range does not exist, plain and simple. That is hard science.

We really are not completely sure about how long it takes nature to make oil, and how long the oil just sits there underground. As to the two step thermal depolymerization, I think this is great, and gets rid of a lot of crap (literally). As to the foul (or fowl) odors, I suspect it is more due to short term storage of raw feed stocks than to the process itself. Moving the process away from concentrated population centers makes some sense, although costs of transport of feed stocks ultimately raises the price of the final products. Other odor controls could be put into place that "renders" the process as fresh and pleasant as an Irish spring on the West Coast of Ireland.

Every farmer should have one of these plants, because virtually every if not every farming operation produces some sort of plant, or animal waste. This would be especially popular in areas with concentrated dairy production.

Probably the reason the thing failed here in the United States is three-fold: (1) if there is an odor it interferes with the sensibilities of a new generation too lazy to even cook for themselves, (2) NIMBY syndrome for anything resembling production of anything useful, and (3) any start-up chemical business on the heels of a weak to non-existent economic recovery (such as the current one) is essentially doomed, since most chemical businesses operate on some of the thinnest profit margins of any of the industries (for good reason, as basis industries).

If one wanted to live in a completely independent, off-grid lifestyle, this certainly beats burning old tires, although there is at least one engineer here who has done it, and has advanced far beyond the other panther units, will be decorated by the leader himself. I would certainly like to have one of these TDP plants in my back yard (if I lived with at least a one mile radius from nearest neighbor). One would still have to drive to town for trash bags and toilet paper once in a while. And don't forget the ammo.

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#32
In reply to #30

Re: CO2 conversion to methanol

02/29/2016 2:03 PM

The report on the process of "turkey guts to oil" dates from 2003. Has anything believable happened since? Or shall we wait a few more geological eras, as before?

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#33
In reply to #32

Re: CO2 conversion to methanol

02/29/2016 4:08 PM

ummmm... did you click/open the second link...?

Lots has been going on in many arenas (including *closing* of the turkey plant, due to foul air... no pun intended, it's inherent)!

"Not my field", so-to-speak; yet, it makes perfect sense to me that monstrous/gargantuan piles of dead carcasses, covered over by deep 'mudslides' (essentially) would naturally form the "heat-under-pressure" so as to decompose into oil in... (let's just say) "something SHORT-OF millions-of-years...

I am NOT saying, here, "the same as", but rather, "in a sort-of-analogous fashion" to the processes going-on whenever spontaneous combustion of hay bales occurs. (but, under all that wet-mud-and-sediments, there ain't enuf O2 to support the combustion... so...)

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#35
In reply to #33

Re: CO2 conversion to methanol

02/29/2016 4:40 PM

Indeed. The second link reports the latest development in 2009 as being:
"The unusual Dutch Auction type IPO failed possibly because CWT has lost nearly $20 million with very little revenue"
I think I will carry on waiting a few geological eras.

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#19
In reply to #4

Re: CO2 conversion to methanol

02/26/2016 8:32 AM

At least when the car breaks down, with ethanol one could theoretically imbibe the fuel for a short time.

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#13

Re: CO2 conversion to methanol

02/25/2016 11:33 PM

I looked at this previously and noting the glaring omission of the necessary H2 figured that some phoney-baloney got through.

There are such things.

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#23

Re: CO2 Conversion to Methanol

02/26/2016 10:02 AM

James Stewart (OP) said:
"They report that the homogeneous Ruthenium catalyst is good for about six cycles of operation."

Where? I only see "the researchers demonstrated that they were able to run the process 5 times with minimal loss of the effectiveness of the catalyst." That may have been all they did. 5 times, how is it holding up?, very well, excellent, report. Is there another article you found on this that says the Ruthenium catalyst takes a big drop off after 6 cycles of operation?

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#24
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Re: CO2 Conversion to Methanol

02/26/2016 12:03 PM

The term "about" is not an absolute term. I suspect they will have problems with the catalyst in the short term, as the number of cycles tested adds up. This is not an insurmountable problem, nes pas? A toute a l'heure!

I wish them all the success in the world, I think it is a good idea, but in a world where oil is cheap, it will be a hard go getting an economic foothold either way.

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#25
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Re: CO2 Conversion to Methanol

02/26/2016 12:15 PM

Also I seem to recall they were running a temperature not far below the decomposition point of the catalyst, about 10 °C lower, so that does not bode for high numbers of cycles of operation.

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#41

Re: CO2 Conversion to Methanol

03/04/2016 12:20 PM

OK, blame me but back to a less "scientific or queasier scientific" approach to this subject. Why would anyone want to convert CO2 to CH3OH with this process when CH4, a very cheap, and certainly less expensive chemical is available as the raw material for a process with the same output chemical?

Good Luck, Old Salt

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#42
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Re: CO2 Conversion to Methanol

03/07/2016 11:21 AM

Old Salt: Just because they can, and apparently, with not was much difficulty as previous generations thought. You are absolutely correct in stating that it is still way cheaper to make methanol from methane.

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