Andrew (cc 2 lists) 

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----- Original Message -----
From: [email protected] 
To: "Discussion of biomass cooking stoves" <[email protected]> 
Sent: Saturday, October 15, 2011 5:31:07 AM 
Subject: Re: [Stoves] Stoves Digest, Vol 14, Issue 17 

On Saturday 15 October 2011 06:56:03 Ron Larson wrote: 
> Trevor, Paul, and lists 
> 
> See Table 1 on p 12 of the draft IBI guidelines, which states that 
> the ash content shall be less than 50%. If you think this is the wrong 
> level, now is the time to speak up. 
> 
> See 
> http://www.biochar-international.org/sites/default/files/IBI_Guidelines 
>_for_Specifications_of_Biochars_for_October_2011_Public_Review.pdf 
> 

Ronal, does this refer to total ash after the sample has been incinerated 
and include ash in the char matrix as well as "free" ash in a partly 
incinerated air starved fire? I can see the desire to not have loose ash 
in a product sold as biochar. 

RWL: I am sure this IBI guideline refers to everything in the "representative" 
char sample that one has been unable to remove by raising a 1 gram sample to 
950C for a specified time period. But the detail is even more specific than 
that - including particle size distribution for the test. 

I should have given the further instructions from IBI's Table 1 for the ash 
test - which says (in full): 

"Apply loss on ignition (ASTM D1762-84) to ascertain 
total non-carbonate ash, then add back inorganic 
carbon as carbonate." 

This standard (like all ASTM standards) costs money. Interested individuals 
might find it available in a local library. But if one googles a little, you 
might find something on the web. What I found and summarized above may not be 
the most current. In a Webinar last week, I heard that alternative tests are 
not permitted - for ash or for anything else. Bit more below. This not being my 
area of interest - I am uncertain on the statement above about inorganics 
(carbonates) - which I don't find in the ATM standard. But the guidelines also 
call for that measurement - so I think there may be some room for confusion 
here (and so am including Kelpie Wilson in this response as well) Re inorganic 
carbon, the pertinent box from Table 1, says: 

"C, H, N analysis by dry combustion (Dumas method), 
before (total C) and after (organic C) HCl addition; 
inorganic C is the difference between total and organic 
C." 

This is undoubtedly clear to those doing this regularly. An example is on the 
last page of the guidelines. 

> > If we gasified all volatile matter, 
> > the fixed carbon content of the char would rise to about 43%, 
> > and the ash content would rise to about 57%. 
> > But typically rice hull biochar has an ash content of about 40%. 
> > This means that there is still a lot of volatile matter that remains 
> > in the biochar. 
> > 


I've still not seen rice husks so take my comments with a pinch of salt. 

I'd be careful about using the term "gasified" in the first sentence, it 
could be taken to mean using sufficient oxygen to deliberately gasify the 
fixed carbon in the husks. If this is done completely then the 
incinerated sample would be 100% ash. 

[RWL: Thanks for this reminder on "gasification". IBI and biomass community 
avoid the word "gasified" - unless they truly are talking about the very small 
amount of material (mostly ash) when one is gasifying (usually to put the gas 
into an engine) and to then get minimum char out. I wouldn't go so far as to 
say that gasifiers give 100% ash - but gasifier folk (and we have a sister list 
doing only that) certainly strive to minimize char. 

A pyrolysed sample would keep all the ash locked in a char matrix. The 
amount of char would depend on the rate of temperature rise ( which we 
could expect to be high in the thin, low mass hulls) and the final 
temperature attained in the treatment 

[RWL: And the input biomass material. I suppose some input biomassmaterials may 
have an inherently difficult time achieving the 50% maximum ash limit , if they 
operate at high temperatures. This is agreeing with your next paragraph. ] 

A typical gasifier would still have some fixed carbon in the ash because 
the air supply is restricted to below that necessary to react out all the 
carbon, because things are not perfect and it is better to discard char 
than have any free oxygen downstream of the gasification process. This is 
the opposite of the internal combustion process where a slight excess air 
is necessary to prevent soot and CO being carried into the exhaust. 

> > In the case of rice hulls, 
> > the amount of volatile matter that remains in the biochar is 
> > determined by the rate of gasification. At times the yield in rice 
> > hull biochar by weight is as low as 30%. At times the yield is as 
> > high as 50%. 

Yes, this I would expect, biochar will consist of two parts, the fixed 
carbon ( which usually is usually dependant largely on lignin content of 
the feedstock and soots redeposited from secondary reactions) and the 
higher temperature tars. These latter are volatilised as temperature 
increases. 

[RWL: And the Biochar community refers to the volatile not-so-permanent part as 
the labile component.] 

> > If the rate of gasification is high, high temperatures within the 
> > reactor are reached. With high temperatures, more volatile matter is 
> > gasified. 

Yes, the heat of burning the carbon raises the temperature and this 
volatilises any surviving tars. 
> > 
> > We need operating temperatures well beyond 1000 C before fixed carbon 
> > gets gasified. 

Well the fixed carbon will remain static above 900C in an airless 
environment but if any oxygen is present it will continue to react with 
any carbon it meets but some carbon will have changed from an amorphous 
form to less reactive graphene like clumps. I'd like to learn more about 
how carbon graphitises with increased temperatures, we know diamond will 
do this but I see little about how biomass derived carbon might undergo 
this change. 

RWL: The ASTM testing talks about 950 C - and probably because little is 
happening even at 900 C. . I too hope to learn more. The experts do a lot of 
this testing with spectrographs. In Kyoto we heard one can learn a lot from 
light reflectivity tests. But indeed more graphene comes with higher 
temperatures. I haven't heard of any correlations with diamonds. 

http://www.bris.ac.uk/Depts/Chemistry/MOTM/diamond/cphased.gif 

shows a phase diagram that suggests at low pressures and high temperatures 
graphite is favoured. 


> > In my opinion it makes little sense to gasify fixed 
> > carbon. 

Then keep air away and quench it fast. 

My question is: why do you want fixed carbon? It is after all a small 
portion of normal charcoal. 

[RWL: Andrew - I was OK with your remarks up to here. I think the meaning is 
/was: let's pyrolyze and end up with char - rather than gasify and end up with 
mostly combustible gases. Can you clarify? We want fixed carbon (charcoal) for 
soil augmentation and carbon sequestration reasons (de-emphasizing energy). Ron 

> > 
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> > than "Re: Contents of Stoves digest..." 

... and please try not to repost whole digests to the list. 

AJH 

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