[Terrapreta] VM composition

[Edward Someus]

Dear Kevin, 
 
Some notice on your question + Michael indicated that VM is not tar. 
 
VM in char is organic residual after incomplete carbonization.  More VM
remaining more incomplete the carbonization process is. Depending on the
input material qty it may  also contain PAH as well, so VM is also indicator
 Most chars on the market containing more or less VM residuals. I made
analytical measurements for many  chars past 20 years for samples world wide
 so far I could not find any char from industrial production, which does not
have some residuals more or less (some suppliers stating that no VM left in
their char, but this statement can not stand an proper analysis). 
 
If gas vapors condensed this is the tar, containing 1000s mixed organic chem
formulas.  In my carbonization system in the 3R I do not condense tar, but I
burn it off gas vapors directly, as tar is an high environmental hazard, and
since synthetic chemical industry is well developed, no real market value. 
 
TEMPEREATURE: in industrial reality this is not the way it works. Although
pyrolysis industry very old and traditional, few modern techniques existing
as carbon processing is of high environmental hazard. Although many large
organizations (over 20 different developments world wide) developed new
generation pyrolysis systems past in the past 25 years and spent BILLIONS of
$, few remaining as viable. 
 
For charcoal production  the big question is where the measured temperature
is, as even if your measure 1000C in the equipment the char may still be at
very low temp heated up such 250-300C only (if heat transfer badly designed)
 so the key is the MATERIAL CORE TEMPERATURE. THIS IS BECAUSE THE BIOMASS IF
VERY BAD HEAT CONDUCTOR.   We can say that 450-500 C material core
temperature reached at industrial level is already reasonably high enough,
as water evaporates at 100 C and thereafter light tars approx. 120 - 185C
and heavy tars 175-285 C, but it takes time and input energy, this is why it
needed over heat treatment, higher than theoretical 285C. 
 

Sincerely yours: Edward Someus (environmental engineer)
Terra Humana Clean Technology Engineering Ltd. 
(ISO 9001 and ISO 14001 certified organization for scientific research,
technical development and industrial performance engineering design of
agro-biotechnological and pyrolysis methods, apparatus and applications) 

ADDRESS: H-1222 Budapest, Szechenyi 59, Hungary
TEL handy:  +(36-20) 201 7557
TEL / FAX:   +(36-1) 424 0224
TEL SKYPE phone via computer:  Edward Someus
WEB:   www.terrenum.net 
-------Original Message-------
 
From: Kevin Chisholm
Date: 2007.06.09. 1:25:36
To: Michael J. Antal, Jr.
Cc: terrapreta at bioenergylists.org;  ENVIPOWER;  'Goro Uehara'
Subject: Re: [Terrapreta] VM composition
 
Dear Michael
 
Isn't it a fact that Tar is a Volatile Material?
 
Would it not be correct to say that all Volatile Matter in charcoal is
not Tar?
 
Isn't it a fact that a "good" charcoal that was produced at say 700C
could have no tar associated with it, but that if it was heated to say
1,000 C, it would evolve Volatile Matter, some of which was tar?
 
It would be helpful if you clarified things a bit for us.
 
Thanks!
 
Kevin
 
Michael J. Antal, Jr. wrote:
> RE: [Terrapreta] VM compositionAs I have emphasized in several previous
> communications, a good charcoal (i.e. a charcoal that you would buy in
your
> grocery store) has no tar in it.  VM is not tar.  I am surprised that this
> misconception continues to persist amongst us.  Regards, Michael.
>
> Michael J. Antal, Jr.
> Coral Industries Distinguished Professor of Renewable Energy Resources
> Hawaii Natural Energy Institute
> School of Ocean and Earth Science and Technology (SOEST)
> 1680 East-West Rd., POST 109
> University of Hawaii at Manoa
> Honolulu, HI 96822
>
> Phone: 808/956-7267
> Fax: 808/956-2336
> http://www.hnei.hawaii.edu
>
>   -----Original Message-----
>   From: ENVIPOWER [mailto:envipower at webspeed.dk]
>   Sent: Thursday, June 07, 2007 10:35 PM
>   To: 'Kevin Chisholm'; 'Michael J. Antal, Jr.'
>   Cc: terrapreta at bioenergylists.org; 'Goro Uehara'
>   Subject: RE: [Terrapreta] VM composition
>
>
>   Dear list
>
>   I joined yesterday and spent a good part of the day trying to get over
the
> archives. Very intense from the start - more political latter. I hope we
can
> stay on the technical side.
>
>   There were some discussions of PAH and other tars contaminating the
soils
> and waters. At the same time there were discussions on the good components
> for microbiological activities.
>
>   If char has been subject to 500 ºC or more, it appears that there will
be
> no environmental harm in the char going into soils. On the other hand it
> also appears from recent postings that Terra Pretta needs the different
> acids, biooils and tars coming from lower temperature treatment.
>
>   It is known that old charcoal manufacturing places are heavily
> contaminated by the tars.
>
>   If charcoal is made between 400 ºC to 500 ºC will it then
>
>   ·       Be the best TP component resulting in highest microbiological
> activies
>   ·       Be the worst TP component since it contaminates the environment
>
>   If charcoal is made between 500 ºC to 600 ºC will it then
>
>   ·       Be absolutely useless as TP
>   ·       Be environmental friendly since all tars are distilled and no VM
> matter is present
>
>   Can we make some conclusions here or am I simplifying too much?
>
>   I would be very pleased to receiving the literature suggested by Michael
> Antal.
>
>   Best regards/Med venlig hilsen
>
>   ENVIPOWER AS
>
>   Nils Peter Astrupgaard
>
>   Snerlevej 1 DK-2800 Kgs. Lyngby
>
>   +45 4061 5600
>
>   npa at envipower.dk
>
>
>
>
>   -----Original Message-----
>   From: terrapreta-bounces at bioenergylists.org
> [mailto:terrapreta-bounces at bioenergylists.org] On Behalf Of Kevin Chisholm
>   Sent: 8. juni 2007 00:27
>   To: Michael J. Antal, Jr.
>   Cc: terrapreta at bioenergylists.org; Goro Uehara
>   Subject: Re: [Terrapreta] VM composition
>
>   Dear Michael
>
>   Thanks very much!!
>
>   Michael J. Antal, Jr. wrote:
>
>   > Dear Kevin: your question is both good, and reflects widely held
>
>   > misconceptions.  A "good" charcoal with a low VM content (< 30%) will
> have
>
>   > experienced a temperature of 500 C or more.  Tars do not survive such
a
>
>   > temperature.  Thus there are no tars present in a "good" charcoal.
>
>   > Furthermore, the VM content of charcoal is not soluble in any common
>
>   > solvent.
>
>   OK... I previously thought that VM was basically tar compounds or
>
>   components that were still within the charcoal, because local
>
>   temperatures were not quite high enough to drive them off. Obviously,
>
>   with "very poor" heating conditions, the wood could still be in the
>
>   cellulose form, or perhaps torrified. What you seem to be saying is that
>
>     the volatile matter in charcoal is NOT at the tar stage, but rather,
>
>   it is wood or degraded wood components that have not been heated to the
>
>   stage where thy have been converted to tars, or other leachable
>
>   material. Is this correct?
>
>   >
>
>   > The VM content is simply a measure of the propensity of the material
to
>
>   > decompose when heated to a high temperature.  Charcoal contains
various
>
>   > functional groups (i.e. carboxy, carbonyl, ketone, lactone, pyranone,
> etc.)
>
>   > that are attached to the carbonaceous backbone structure of the
charcoal
> and
>
>   > are not stable at high temperatures, decomposing to form CO2, CO, CH4,
> H2,
>
>   > etc when heated.  These functionalities are the "VM content" of the
>
>   > charcoal.
>
>   I am embarrasingly weak on Organic Chemistry. To restate the above,
>
>   would it be correct to say "The above functional groups are what cause
>
>   Volatile Matter in charcoal, and they are not soluble in any common
>
>   solvent. When heated adequately, they will decompose to CO2, CO, CH4, H2
>
>   and tars which are swept away."
>
>   Given that the above is basically correct, and that some of the
>
>   "functional groups" were decomposed, but not all, would there be
>
>   "leachable tars" in such charcoal?
>
>    From a practical standpoint, it is easy to see if I produce "poor"
>
>   charcoal... I can see areas of unchanged wood or wood which was
>
>   torrified or darkened. I don't need any tests to tell the batch was bad.
>
>   If I produced a charcoal that had no original wood, or browned wood,
>
>   such that I felt it was a "good low temperature charcoal", would it
>
>   contain any leachable VM?
>
>   >
>
>   > If you are interested in further details, please contact me and I can
> send
>
>   > you two technical papers on this subject that were recently accepted
for
>
>   > publication in IECR.  One of these papers offers details of the actual
>
>   > functional group structures that compose carbonized charcoal.
>
>   Thanks very much!! I will contact you off line.
>
>   >
>
>   > Regards, Michael.
>
>   >
>
>   > P.S. Tars formed from biomass and cellulose are easily dissolved in
>
>   > methanol, ethanol, or acetone.  We prefer to use ethanol.
>
>   I happen to have acquired about 30 gallons of Iso-Propyl Alcohol. How
>
>   would you rate this as a tar solvent?
>
>   Thanks very much for your help.
>
>   Kevin
>
>   >
>
>   > -----Original Message-----
>
>   > From: Kevin Chisholm [mailto:kchisholm at ca.inter.net]
>
>   > Sent: Wednesday, June 06, 2007 12:27 PM
>
>   > To: Michael J. Antal, Jr.
>
>   > Cc: peter; terrapreta at bioenergylists.org; Tom Miles
>
>   > Subject: Re: [Terrapreta] I wish to unsubscribe
>
>   >
>
>   >
>
>   > Dear Mike
>
>   >
>
>   > I reviewed the two postings you made to the Terra Preta List since its
>
>   > inception, and I wonder if perhaps you comment on the following point
>
>   > before you leave?
>
>   >
>
>   > Michael J. Antal, Jr. wrote:
>
>   >  > Dear friends: the VM content of cellulose is about 90% but it does
> not
>
>   >  > dissolve in terpentine.  Need I say more?  Michael.
>
>   >
>
>   > Would not the VM components in Charcoal most likely be tars, and
>
>   > products of decomposition of cellulose, rather than cellulose?
>
>   >
>
>   > Would tars and and the decomposition products of cellulose that are
>
>   > found in charcoal be soluble in turpentine?
>
>   >
>
>   > Do you know of any other common solvents that could be used to
dissolve
>
>   > tars resulting in he charcoal making process, or able to dissolve
other
>
>   > cellulose decomposition products that one might expect to find in
>
>   > charcoal that contained volatiles?
>
>   >
>
>   > Thanks very much.
>
>   >
>
>   > Kevin
>
>   >  >
>
>   >  > Michael J. Antal, Jr.
>
>   >  > Coral Industries Distinguished Professor of Renewable Energy
> Resources
>
>   >  > Hawaii Natural Energy Institute
>
>   >  > School of Ocean and Earth Science and Technology (SOEST)
>
>   >  > 1680 East-West Rd., POST 109
>
>   >  > University of Hawaii at Manoa
>
>   >  > Honolulu, HI 96822
>
>   >  >
>
>   >  > Phone: 808/956-7267
>
>   >  > Fax: 808/956-2336
>
>   >  > http://www.hnei.hawaii.edu
>
>   >  >
>
>   >  >   -----Original Message-----
>
>   >  >   From: terrapreta-bounces at bioenergylists.org
>
>   >  > [mailto:terrapreta-bounces at bioenergylists.org]On Behalf Of Sean K.
> Barry
>
>   >  >   Sent: Tuesday, April 24, 2007 5:01 PM
>
>   >  >   To: Tom Miles; 'terrapreta'
>
>   >  >   Subject: Re: [Terrapreta] Agrichar trialled in field at
Wollongbar
>
>   >  >
>
>   >  >
>
>   >  >   Hi Tom,
>
>   >  >
>
>   >  >   I believe that volatile matter in charcoal is all easily
dissolved
> by
>
>   >  > turpentine.  Turpentine is itself one of the liquids, which are
> distilled
>
>   >  > from wood (a fractional distillate).  Turpentine might however be
> left on
>
>   >  > charcoal if you were to attempt to wash VM from the char.
>
>   >  >
>
>   >  >   The ASTM standard D1762 measures VM% on w/w basis weight.  It
does
>
>   > not use
>
>   >  > a solvent and the actual VM is lost in the test procedure
>
>   >  >   (it evaporates).  So it will only get at the weight of the VM or
> VM% of
>
>   >  > the charcoal on a w/w basis.
>
>   >  >
>
>   >  >   Maybe a procedure could be developed to wash VM from charcoal
with
>
>   >  > turpentine, measure the weight of the VM which was washed out, and
>
>   > actually
>
>   >  > have the VM (in solution with the turpentine).
>
>   >  >
>
>   >  >   1) Dry a pulverized charcoal sample at 105 degrees C for some
hours
> (or
>
>   >  > until it no longer loses weight).
>
>   >  >   2) Add a measured (weight) amount of turpentine to the charcoal
> (for a
>
>   >  > wash) in a sealed container.
>
>   >  >   3) Weigh the wash solution with the charcoal together after some
>
>   > period of
>
>   >  > washing agitation.
>
>   >  >   4) Pour out the wash solution (containing turpentine and VM)
>
>   >  >   5) Drive off the turpentine left on the charcoal by bringing its
>
>   >  > temperature up to the boiling temperature of turpentine for some
> minutes.
>
>   >  >   6) Weigh the cleaned (of VM) and dried (of turpentine) charcoal.
>
>   >  >   7) The weight of the VM should then be;
>
>   >  >       weight of wash solution and charcoal (step 3) - weight of
>
>   > cleaned and
>
>   >  > dried charcoal (step 6) - weight of turpentine (step 2)
>
>   >  >   8) The Volatile Matter itself will be in solution with the
>
>   > turpentine in
>
>   >  > the post wash solution.
>
>   >  >
>
>   >  >   If the procedure was tried on duplicate samples, one with ASTM
>
>   > D1762 and
>
>   >  > one with the test procedure I proposed, then the resulting %VM
>
>   > numbers could
>
>   >  > be compared.  If they match closely, then I think it would be safe
to
> say
>
>   >  > that the total measurable VM can be "washed" from the charcoal
sample
> by
>
>   >  > using the procedure.
>
>   >  >
>
>   >  >   I think this could work.  Then the actual VM could be further
> analyzed.
>
>   >  > This presumes that the turpentine does no chemically react with the
> VM
>
>   >  > (other than to dissolve it).  I'd welcome any comments from anyone
>
>   > who might
>
>   >  > think it won't work for any reason.
>
>   >  >
>
>   >  >   Regards,
>
>   >  >
>
>   >  >   SKB
>
>   >  >     ----- Original Message -----
>
>   >  >     From: Tom Miles
>
>   >  >     To: still.thinking at computare.org ; 'Sean K. Barry' ; 
terrapreta'
> ;
>
>   >  > 'Michael Bailes'
>
>   >  >     Sent: Tuesday, April 24, 2007 6:53 PM
>
>   >  >     Subject: Spam: RE: [Terrapreta] Agrichar trialled in field at
>
>   > Wollongbar
>
>   >  >
>
>   >  >
>
>   >  >     Duane, Sean, Michael,
>
>   >  >
>
>   >  >
>
>   >  >
>
>   >  >     These are good references. The ash composition of the woods,
> grasses,
>
>   >  > pulping residues, sludge, etc. will carry varying quantities of
>
>   > nutrients to
>
>   >  > the degree that they are retained in the char. Through studies like
>
>   > these we
>
>   >  > know more now about the volatility of the inorganics (K, S, Cl)
> during
>
>   >  > pyrolysis, gasification and combustion.
>
>   >  >
>
>   >  >
>
>   >  >
>
>   >  >     I was referring primarily to measuring the volatile matter (VM)
>
>   > that is
>
>   >  > apparently available to the organisms which is what Steiner must
have
>
>   > been
>
>   >  > referring to as the bio oils that are retained in the char. If a
char
> has
>
>   >  > 10%,  20% or 40% VM is it all available to the organisms or some
> portion?
>
>   >  > How do we measure that? Is the VM that is available soluble in a
> dilute
>
>   >  > acid?
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