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S.C. Wack
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Looked up reference 2 in the paper that I linked to - in Chem. Lett. 33, 282 (2004), the most ideal conditions for benzene in that system were: PET
powder was heated with Ca(OH)2 at 700C at a 10:1 Ca(OH)2 : PET ratio, giving a distillate that was 45.5% of the weight of the PET, and benzene
accounted for 36% of the weight of the PET.
They analyzed the products closely and quantitatively under the various parameters used, and quite a number of things were present. Under the ideal
conditions, the highest % contaminants of the distillate were, again in wt.% of PET: 3.5% biphenyl, 2.3% toluene, 1.36% styrene, and 0.6%
acetophenone. Using any less, and especially much less Ca(OH)2, dramatically decreased the selectivity for benzene.
[Edited on 25-7-2009 by S.C. Wack]
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JohnWW
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But, on an industrial scale, how would such a process for obtaining benzene, based on hydrolysis of PET (probably from recycled plastic drink bottles,
most of which BTW are shipped to China) and decomposition of the monomeric products thereof, compare for unit co$t and efficiency with either
fractionation of benzene from petroleum, or direct synthesis of benzene by polymerization of acetylene under heat and pressure? (The acetylene, C2H2,
having been generated by hydrolysis of calcium carbide, CaC2, obtained by pyrolysis of lime with coke or anthracite in a retort). As a chemical
engineer, I am aware of such considerations.
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Zinc
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Sorry if this is a little off topic, but is there any way toluene could be obtained by some pyrolysis procedure like benzene can?
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Picric-A
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Yes, heating 2-methyl-benzoic acid with NaOH will produce toluene
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Eclectic
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Does anyone know if benzenesulfonic acid would distill (190 C) from benzoic acid in hot sulfuric acid as a decarboxylation solvent? Perhaps with a
little copper as catalyst?
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manimal
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Apparently, Org recently passed away from cancer. One wonders if his fondness for chemicals such as this played a part.
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Jor
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Org? Organikum? What kind of cancer?
Whoever it was, rest in peace!
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manimal
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Seconded.
Organikum, yes; I'm not sure of the details, that's just what I read on another forum (WD).
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hissingnoise
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It's saddening to note that our clandustrial priest won't be posting again.
I hope he enjoyed his life.
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S.C. Wack
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IIRC he mentioned a terminal lung cancer diagnosis (he was a smoker) in passing in his deliberately last post there in a threat --- about 5 months
before his last post here. Note how the last login here is much later. IDK if he said anything in whimsy here that no one noticed, if he hated the RIP
Halfapint thread at the-hive, or what the deal is. Anyone that knows for sure isn't saying.
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unionised
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I just looked through this thread and didn't see a reference but has anyone considered the pyrolysis of polyvinyl acetate (or alcohol) as a synthetic
pathway to benzene?
Pyrolysis of PVC works too, but I'd not be happy about the potential for making chlorinated aromatics.
Not sure how well this link will work, but it indicates that benzene is a major product (based on gc peak area which isn't a brilliant way to quantify
stuff)
http://books.google.co.uk/books?id=AY__YWnIE_4C&pg=PA312...
There's a table of products on p326.
[Edited on 25-4-10 by unionised]
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densest
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Sort-of-on-topic: I heard about a company in Houston which is using large plasma reactors to reprocess waste such as PET, other
plastic scraps, and about anything else which can be vaporized in their chambers, the output being fractionated with (I am guessing) MHD or other very
large scale electric-magnetic-mass-??? separators.
I'm trying to track this down... google didn't have anything suggestive last time I looked. Any rumors anywhere?
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not_important
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http://en.wikipedia.org/wiki/Plasma_arc_waste_disposal
http://www.popsci.com/scitech/article/2007-03/prophet-garbag...
While aromatics are formed in high temperature mixes rich in carbon and hydrogen in roughly unity ratio, SFAIK the yield generally aren't great and
you tend to get mixtures.
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Sandmeyer
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Quote: Originally posted by S.C. Wack  | | IIRC he mentioned a terminal lung cancer diagnosis (he was a smoker) in passing in his deliberately last post there in a threat --- about 5 months
before his last post here. Note how the last login here is much later. IDK if he said anything in whimsy here that no one noticed, if he hated the RIP
Halfapint thread at the-hive, or what the deal is. Anyone that knows for sure isn't saying. |
Is it true that he is dead? If it is true then it is a great loss to internet chemistry forums. I truly miss his posts and his sense of humour, to
hear that he is no longer here is very saddening.
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majortom
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| Quote: Originally posted by BASF | Do you have more information on the decarboxylation of benzoic acid?
Decomposition temp. and similar things?
I think the decarboxylation of benzoic acid would be very attractive for the home chemist due to the widespread use of benzoic acid in the food
industry, and therefor it should be easy to get and not that expensive.
I still have some 100-200g of benzoic acid from a drug store.
HLR |
Wikipedia has an interesting article on benzene in soda, not very much mind you but it is still benzene. It was apparently caused by decarboxylation
of benzoic acid.
http://en.wikipedia.org/wiki/Benzene_in_soft_drinks
I have heard of thermal decarboxylations on amino acids, I have heard that ketones act as catalysts and increase yields, It used Tryptophan or Lysine
in xylene with a dash of MEK (2-butanone) I am not sure what yields are or if the ketone does anything at all. Although the wiki article says citric
acid and some other things in citrus soda's catalyze the reaction of benzoic acid.
[Edited on 8-5-2010 by majortom]
[Edited on 8-5-2010 by majortom]
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not_important
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that has been brought up before, the amounts formed are microscopic.
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majortom
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Diffidently, only a few micrograms but if the reaction can take place, albeit slowly, in soda in a very cool temp(even if it is 100 F) than what would
happen if we heated it up to 150 C in some high boiling point solvent?
[Edited on 9-5-2010 by majortom]
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bfesser
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Thread Topped
3-10-2013 at 09:45 |
testimento
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I am unfortunate to not to be able to find data which could indicate how xylene or benzene could be transferred to toluene. Does anyone have any data
or sources for this process?
I found one possible route:
p-Toluic acid is first made from xylene with KMnO4, and then it is decarboxylated with 2 moles of NaOH, leaving toluene and sodium carbonate residues.
[Edited on 20-10-2013 by testimento]
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amazingchemistry
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It might be possible to form benzene via decarboxylation of benzoic acid. The main article cited in wikipedia, from the Journal of Agricultural and
Food Chemistry, does not make a thorough effort to find the best conditions for benzene synthesis, as it's goal is to find out whether decarboxylation
occurs in realistic beverage storage and consumption conditions. And indeed it does, albeit in microscopic amounts, as has already been pointed out.
I'm curious if yield could be improved by heating/refluxing, by finding a better decarboxylating agent (ascorbic acid is used, citric acid is also
mentioned but this produces even lower yields), or by finding a better transition metal catalyst (mainly iron and copper compounds are used). I've had
this in mind for months now, but unfortunately, I can't afford the equipment or reagents to test this, or find a suitable place to carry out these
experiments.
Always remember to check your pride at the door and ask that "stupid" question. Learning comes from having your "stupid" questions answered.
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DJF90
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Have you not bothered reading this thread?? Benzene was fairly easily obtained by this route. A friend of mine did this to make over 3 L of benzene.
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amazingchemistry
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By "fairly easily" do you mean by the high-temperature solid-solid distillation of benzoic acid and sodium hydroxide? The same distillation where you
have to be very careful temperature-wise or your glassware melts on you (molten hot NaOH being death to glass)? Do you mean the same distillation that
because of this, more often than not, requires all-metal setups (many of which are pictured in this and other threads)? Do you mean the same
distillation that yields an unsightly red product that you have to redistill to get anything close to pure benzene? Or have we made progress in the
couple of months I've been away from this forum? If you bothered to read the paper in question you'd know that this particular decarboxylation was
achieved in an aqueous solution of sodium benzoate, maintained at pH 2 with a buffer, using ascorbic acid as a hydroxyl radical donor and a transition
metal catalyst. There was some decarboxylation going on even at room temperature. No need for homemade metal setups, crazy temperatures, etc. Although
the reported yield is very small at typical beverage storage and consumption conditions, the paper did make me think about whether efficient benzene
synthesis can be achieved by this route, given optimized reaction conditions. This is a valid research question, but unfortunately I have neither the
equipment nor the place to pursue it. Maybe others can?
[Edited on 21-10-2013 by amazingchemistry]
Always remember to check your pride at the door and ask that "stupid" question. Learning comes from having your "stupid" questions answered.
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Lambda-Eyde
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Decarboxylations can be done at lower temperatures with other reagents. Here is an example. Although I see no reason to abandon the current established route, as NaOH is dirt cheap and readily available and the
procedure itself is piss easy for anyone who has a spare paint can.
This just in: 95,5 % of the world population lives outside the USA
You should really listen to ABBAPlease drop by our IRC channel: #sciencemadness @ irc.efnet.org
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amazingchemistry
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I don't see a reason to abandon the current route either (after all, we know it works). However, as far as I know, no experiments have been done to
explore whether the above route or other routes would be feasible, or perhaps even better than the current one. I'm interested in the route described
above because both ascorbic acid and sodium benzoate are cheap and readily available, and because the procedure described in the paper amounts to
little more than 'mix and heat.' If that doesn't work, maybe we can learn something from it. We're chemists after all, and most of the stuff we do
doesn't work 
Always remember to check your pride at the door and ask that "stupid" question. Learning comes from having your "stupid" questions answered.
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DJF90
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In such simple terms, thats exactly what the current method is.
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testimento
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What might be the easiest way to oxidize styrene, toluene or xylene into benzoic acid?
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