Biochemicals from Pyrolysis

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courtesy: Wytze Meindersma, Eindhoven University of Technology, found here

Liquids derived from the pyrolysis of biomass, also known as bio-oil, may contain hundreds of different organic chemical substances. Some of these can be quite valuable and therefore simply using the vapors and liquids only for energy (example: burning in a Babington Burner) may be wasteful. Depending on the amount of gases/bio-oil produced, it may be worthwhile to separate out the complex organic chemicals from simpler ones.

Components

The spectrum of chemicals varies with feedstock and conditions, such as gasifier temperature, rapidity of temperature increase, duration, pressure etc.

The vapors that come off can be sent into another drum, submerged in cool water for condensation to occur.

Other components include:

• organic acids (formic acid, acetic acid, propionic acid, butyric acid, etc);
• phenol group;
• carbonyl group (formaldehyde, acetaldehyde, etc.);
• alcohol (ethanol, methanol, etc);
• neutral materials (levoglucosan, acetol, maltol, etc);
• base (substances like ammonia, methylamine, dimethylamine, etc.)

One major component from the dry distillation of wood is acetic acid, which has many applications and can even be used as an organic herbicide. Methanol is another useful and frequent component. Upgrading of methanol to biodiesel is possible but may not be practical or even necessary (methanol IC engines are already widely being used).

After pyrolysis, the vapors are first cooled down for distillation. As coolants, water or external air may be used. Gaseous components (primarily carbon monoxide, hydrogen and methane) remain gases and can be flared. The liquid phase is then diluted with water, which leads to separation into a polar/aqueous and apolar/oily layer. Simple, low-tech, open-source methods of separation are needed.

Is extraction worth the trouble ?

The alternative to extraction is always to use these substances for their energy content. So rather than extract the apolar biochemicals from the oily phase, it may make more sense to mix all or some of them with (bio-)diesel (see this page for more details (and reference: [1]. Similarly, if it is not worth extracting the sugars from the aqueous phase, they can possibly be fed into an alcoholic fermentation stream, producing ethanol, or into an anaerobic fermenter to make biogas.

Syngas Fermentation

An interesting new development are biological methods for the catalysis of CO and H to ethanol. This is one application of the emerging field of syngas fermentation. Companies such as Coskata and Enerkem are turning the various syngas components into ethanol using microbes in a bioreactor. This demonstrates a useful principle: distillation products are further processed using (micro-)biological means. Unfortunately, this field is littered with patents and will not become open source any time soon.

Possible Applications

• the classic: wood preservative [2]
• organic acids (e.g. formic acid, acetic acid)
• sugars, flavors
• pharmaceuticals
• bioplastics
• fibers, resins, dyes, adhesives

Possible Feedstocks

• various kinds of biomass (corn stalks, straw, wood, leaf litter, algae)
• manure incl. humanure
• animal waste, bones

Important considerations

• The big question is: can this be scaled DOWN to village-scale in a practical way ? If so, the products (incl. biochar from pyrolysis) may become important sources of revenue for the community. Being able to create a large number of different potential products with a single separation mechanism would be significant in terms of autonomy and resilience.
• which feedstocks produce which biochemicals in reasonable quantity ? under what pyrolysis conditions ?
• gasifier design / pyrolysis conditons etc.
• distillation and separation of products; one extraction method is using methanol as a solvent [3]
• further processing of products: when used for energy, purity may be less important then when used for pharmaceuticals (for example).

Possible OSE Protocol (under development and up for debate)

The goal here is to develop a simple, robust, low-cost, low-energy, (low-tech ?) way to extract certain biochemicals from biocrude. The process really already starts at the time of pyrolysis, since its conditions have major effects on the composition of the resulting bio-oil. Abundant solar process heat may be available and can be used for distillation and other steps.

1.) Cool the pyrolysis vapors by running them through a coil (copper ?, glass ?, not steel - the vapors are corrosive !) which is immersed in coolant water. This separates out the gaseous components, namely CO, H2, CO2 and some CH4 from the liquid. Use these gases for energy (heat), perhaps to boil water, turn into steam. Consider a heat recovery system that will later use this coolant water in a steam engine (after further heating and boiling)
2.) Dilute the resulting liquid portion with water and let settle - this separates the polar aqueous phase from the apolar oily phase; filtration will be required. The aqueous phase has some highly acidic components, such as formic acid and acetic acid. Let it settle, this step takes a bit of time. There are still volatiles in the liquid which evaporate over time (this has environmental, energy yield and health implications).
3.) So far, so good, but then it gets more complicated (depending on the bio-oil composition, goals of extraction, etc.). The apolar/oily phase has lighter and heavier components - and is therefore possibly amenable to fractional distillation, for which an open source model could be developed.

Relevant Expired Patents

• LEVOGLUCOSAN PRODUCTION BY PYROLYSIS OF PRETREATED STARCHES
• Method and apparatus for converting solid organic material to fuel oil and gas

Links

• excellent, very detailed presentation: "Separation of chemicals from pyrolysis oil" by Wytze Meindersma, Eindhoven University of Technology, part of "Biocoup" - Co-processing of upgraded bio-liquids in standard refinery units