Welcome to PyroWiki
Generally, pyrolysis is the thermochemical decomposition of organic material at elevated temperatures in absence of oxygen. It involves the simultaneous change of chemical composition and physical state, and is irreversible. The word is coined from the Greek-derived elements pyro "fire" and lysis "separating".
The focus of this Wiki is on fast pyrolysis using ligno-cellulosic biomass and residues as feedstock, primarily with the aim to maximize the liquid product yield. Fast refers to the fast/rapid heating of the biomass particles. The resulting liquid can be used as fuel, energy carrier or feedstock for further processing. PyroWiki aims to cover all aspects related to the technology and product use.
- 1 History of fast pyrolysis
- 2 Why fast pyrolysis of biomass?
- 3 Fast pyrolysis principle
- 4 Properties of fast pyrolysis liquid
- 5 Fast pyrolysis technologies
- 6 Catalytic Fast Pyrolysis
- 7 Implementation
- 8 Fate and role of minerals
- 9 Applications of fast pyrolysis liquid
- 10 Biomass feedstock
- 11 Sustainability
- 12 Standards, Norms & Legislation
- 13 Transport of pyrolysis oil
- 14 Acknowledgement
- 15 References
- 16 Getting started
History of fast pyrolysis
The word “pyrolysis” is used for the degradation of a substance upon exposure to high temperatures. Exclusion of air of oxygen is essential in case ignition and combustion of the primary products is considered undesirable. Slow pyrolysis of wood at temperatures up to 400 degrees centigrade is a process that has exploited for thousands of years. Charcoal is a smokeless fuel that is still used widely for cooking and heating purposes. It has been used industrially as well, viz. in blast furnaces for the making of iron. A further description on pyrolysis can be found elsewhere
Before the eighties of the last century, 'fast' pyrolysis research was mostly dealing with the thermal decomposition of organic compounds, polymer, salts, etc. Quite a number of papers can be found regarding coal pyrolysis (production of metallurgic coke), and some on the pyrolysis of oil shale. In the field of biomass fast pyrolysis no more than 10 scientific publications can be found for the period 1955 to 1980. Cellulose, one of the main biomass constituents, was investigated quite frequently, but merely in relation to flame retardation purposes. Likewise, some lignin pyrolysis studies can be traced back, because wood chemistry scientists were interested in the analysis of lignitic vapors in particular. A single publication is found when using the keywords “biomass fast pyrolysis”; the hit refers to the abstracts of papers of the American Chemical Society made available to its members in 1980. A short historical review on biomass fast pyrolysis was published by Radlein & Quignard 
The research and development of biomass fast pyrolysis started around 1980, when the Solar Energy Research Institute (today NREL) organized a specialists’ workshop on fast pyrolysis of biomass in Copper Mountain, Colorado.  Founders of various fast pyrolysis technologies were part of research groups pioneering in the development of reactor technology during the eighties and nineties of the past century.
Why fast pyrolysis of biomass?
The production of pyrolysis oil is an efficient method to utilize biomass as a renewable energy resource for energy, chemicals and/or materials. Raw biomass is mostly collected from distant areas in relatively small quantities. Besides, the biomass is often difficult to handle due to unfavourable properties like:
- a fluffy structure and low volumetric density
- the presence of contaminants such as sand and ash
- a high moisture content
- a complex chemical structure, built up mainly from cellulose , hemicellulose and lignin.
In fast pyrolysis a uniform liquid is produced with improved properties. It enables the distributed production of pyrolysis liquids at a relatively small scale and in remote areas, for centralized utilization elsewhere at a much lager scale and any desirable time. In this way, the biomass usage is fully decoupled (time & place) from its production. The improved properties enable a more efficient transport and processing if compared to the original biomass.
Fast pyrolysis principle
Pyrolysis is a process in which organic materials are heated in the absence of air/oxygen. Under these conditions the organic material decomposes, forming vapors, permanent gases and charcoal. The vapors can be condensed to form the main product: pyrolysis liquid. In order to maximize the liquid production, the biomass heating as well as the vapor condensing needs to be done quickly. Hence the name fast pyrolysis. Alternatively, the biomass conversion can be directed at producing charcoal. In this case heating is less rapid and the process is called slow pyrolysis or carbonisation. The latter is usually carried out at temperatures below 400 degrees centigrade.
Fast pyrolysis is meant to convert the biomass to a maximum quantity of liquid of around 60 to 70 wt.% of the feedstock. Beneficially, a more uniform, stable and cleaner-burning product is obtained, that could serve as an intermediate energy carrier and feedstock for subsequent processing. The essential conditions of fast pyrolysis for the production of pyrolysis liquids are:
- a very fast heating of relatively small biomass particles (order of seconds)
- controlling the pyrolysis reactor temperature at a level around 500 degrees centigrade
- a short vapour residence time to avoid further cracking to permanent gases
- rapid cooling of all the vapors to form the desired pyrolysis liquid.
By-products in the form of char and non-condensable gases are produced as well. In an industrial process, these two by-products (both 10 to 20 wt.%) would be used primarily as a fuel for the generation of the required process heat (including feedstock drying). But sometimes the char is also proposed to be applied as a (‘biochar soil improver’) or as a substitute for metallurgic coke in the steel industry. Alternatively, for specific purposes (and reasons), it can be recombined with the fast pyrolysis oil to form a char-oil slurry (for example the BioLiq process and formerly Dynamotive's Bio-oil Plus). The gaseous by-product essentially is a mixture of CO and CO2. Apart from possible flue gas emissions resulting from the char combustion, there are no waste streams. The biomass ash will be largely concentrated in the char by-product. It is separated when the char is combusted in the process, viz. to generate the heat for drying and heating of the biomass feedstock. Ash separation enables recycling of the minerals as a natural fertilizer to the soil on which the biomass was grown originally.
More details on the Main Principles of Fast Pyrolysis of biomass are given elsewhere.
Properties of fast pyrolysis liquid
Fast pyrolysis liquid is a mixture of many different components, and a unique definition is lacking. One definition of the desired pyrolysis liquid or Fast Pyrolysis Bio-Oil (FPBO) has been given by the IEA Bioenergy task 34 members.
|Liquid condensate recovered by thermal treatment of lignocellulosic biomass at short hot vapour residence time (typically less than about 5 seconds) typically at between 450 – 600 °C at near atmospheric pressure or below, in the absence of oxygen, using small (typically less than 5 mm) dry (typically less than 10% water) biomass particles. A number of engineered systems have been used to effect high heat transfer into the biomass particle and quick quenching of the vapor product, usually after removal of solid by-product ”char”, to recover a single phase liquid product. Bio-oil is a complex mixture of, for the most part; oxygenated hydrocarbon fragments derived from the biopolymer structures. It typically contains 15–30% water. Common organic components include acetic acid, methanol, aldehydes and ketones, cyclopentenones, furans, alkyl-phenols, alkyl-methoxy-phenols, anhydrosugars, and oligomeric sugars and water-insoluble lignin-derived compounds. Nitrogen- and sulfur-containing compounds are also sometimes found depending on the biomass source.|
Pyrolysis liquid is a dark-brown, free flowing, oil-like substance with a pungent odor and several distinctive properties. While it is usually called pyrolysis oil, here the term pyrolysis liquid (PL) is used to avoid any confusion with fossil oils. Ligno-cellulosic biomass derived PL essentially contains 20 to 30 wt% water and fragments of the cellulose, hemicelluloses, lignin, and extractives. The organics in PL include hundreds of different compounds with various functionalities (e.g. ketones, aldehydes, sugars, acids, phenols, aromatics, extractives etc). The density of pyrolysis liquid is near 1.2 kg/l and its lower heating value is 15 to 17 MJ/kg. The corresponding crude oil values are 0.85 kg/l and 42 MJ/kg respectively. PL therefore contains 40% of the energy of crude oil on weight basis, and roughly 60% on a volumetric basis. Pyrolysis liquid is acidic with a pH of 2.5 to 3, due to the presence of organic acids. The analysis of the liquid is not straightforward as many of the analysis methods developed for fossil oil can not be applied directly.   and analytical methods needs to be validated.
Fast pyrolysis technologies
Various fast pyrolysis technologies have been developed over the last decades on basis of different reactor types . The essential characteristics of a fast pyrolysis reactor for maximal oil production are the very rapid heating of the biomass, an operating temperature around 500°C, and a rapid quenching of the produced vapors. In small dedicated laboratory reactors high oil yields can be obtained when very small particles are used while imposing high heat (and mass) transfer rates, and low vapor residence times. In real scale installation however, the consequences of heat transfer limitations and excessive vapor residence times may be significant.
Indeed, high interparticle heat transfer rates are required (heat transfer coefficients of more than 500 W/m2K). Moreover, intra-particle biomass heat transfer limitations should be avoided, which would require particles sized to less than 3 mm for the effective heat penetration depth. Vapor phase residence times should be kept within a few seconds in order to maintain the oil yield. In case a pyrolysis plant is meant to produce a liquid fuel for combustion or gasification, the process could be designed in a way that maximizes the energy conversion to the liquid product. However, when the bio-oil product is meant to derive bio-fuels or chemicals from it (see one of the next paragraphs), other factors than just the vapor residence time should be considered as well. The composition of the oil obviously depends on the type of feedstock used, but can be steered further by process conditions, equipment dimensions and the application of catalysis.
Several fast pyrolysis technologies have been developed (on laboratory-, pilot, demo or commercial scale); One way to distinguish the different technology is on basis of the type of reactor or mixing employed:
- Fluidized bed
- Circulating fluidized bed
- Auger reactor
- Rotating cone
- Vacuum, and
- New Developments
Catalytic Fast Pyrolysis
The pyrolysis liquid derived from fast pyrolysis by just a thermal treatment is a mixture of hundreds of different, highly oxygenated chemical compounds. A growing interest and activity is noticed on Catalytic Fast Pyrolysis (BIOBOOST,CASCATBEL). This catalytic pyrolysis is seen as a promising route to yield liquids of a higher quality, and catalysis could indeed be applied for a number of reasons, and at different positions in the process. Objectives are e.g. improved chemical and physical stability, high yields of target compounds, and improved miscibility with refinery streams. An appealing example from the recent past is the KIOR plant which was meant to commercially produce 40,00 ton drop-in transportation fuel annually, via catalytic fast pyrolysis. The company however never reached their production targets and eventually felt into bankruptcy; the IP was transferred to Inaeris Technologies. Literature data show that, when using a zeolite type of catalyst, the most reactive components are quickly converted to coke, gas, and water, while only a limited yield of liquid products (mostly phenols and aromatics) is obtained. The diagram shown here is adopted from . It illustrates how for various biofuel production routes the final deoxygenation degree correlates with the overall carbon yield. For catalytic pyrolysis the results are quite poor: in case of a high degree of deoxygenation, the carbon yields are extremely low. Whether or not this can be improved by developing more efficient catalysts (for instance with an increased meso-porosity) or a better process control, is still obscure. Meanwhile it has been reported that the application of pressurized hydrogen, viz. in the IH2 process developed by IGT  and licensed to CRI catalyst company, leads to a significant improvement in product yield and quality when a close-coupled hydro-treating of the pyrolysis vapors is applied before condensation. A relatively new company called Annelotech  is focusing on the production of benzene, toluene and xylenes (BTX) as aromatic chemicals. Obviously the application of pressure and the consumption of hydrogen adds to the costs of catalytic pyrolysis. It complicates the pyrolysis process such that it would be bound to well-developed industrial sites and relatively large scales of operation. As an alternative one could also hydro-treat a crude bio-oil after its transportation to a central facility. Catalytic post-treatment of the liquid is discussed elsewhere in this PyroWiki, see Biofuels.
During the 1980s and the early 1990s, various reactors were invented and tested in US, Canadian and European laboratories. Amongst them are the vortex reactor, rotating blades reactor, rotating cone reactor, cyclone reactor, transported bed reactor, vacuum reactor, and the fluid bed reactor. From the late nineties the process development emerged, resulting in the construction of pilot plants in Spain (Union Fenosa), Italy (Enel), UK (Wellman), Canada (Pyrovac, Dynamotive), Finland (Fortum) and The Netherlands (BTG). Due to various reasons, these pilot plants are not in operation anymore; some of them were not even started (Wellman, Pyrovac). BTG however always continued to use their pilot plant for both, research projects and industrial clients. In the US and Canada, Ensyn’s circulating fluid bed bed process (approx. 1 t/h) has been used for many years in the commercial production of “liquid smoke”, a food flavor that can be extracted from the pyrolysis oil. The alliance of Ensyn with UOP resulted in a new company called Envergent, which aims at production and sales of biofuels. Dynamotive built large installations in West Lorne and Guelph, respectively of 3 and 6 t/h biomass throughput, but never succeeded to demonstrate its technology. The installations were meant for the utilization of bio-oil in heat and electricity production. Now they are dormant (West Lorne) and dismantled (Guelph). A recent update of ongoing activities have been given by IEA Task 34. In the bullets below, a list with pyrolysis production units can be found.
Fate and role of minerals
An advantage of fast pyrolysis is the separation of inorganic compounds from the main liquid product. Typically, more than 95% of the minerals in the original biomass end up in the char. However, the presence of these minerals in the biomass do effect the performance of the pyrolysis process in a negative way (i.e reduced yield, increased water content). Certain minerals - in particular alkali based salts- can also cause operational problems like slag formation. To minimize the negative effect of these minerals on fast pyrolysis process biomass pretreatment like washing is considered.
For more information, see minerals in pyrolysis
Applications of fast pyrolysis liquid
Heat & Power
Fast Pyrolysis liquid can be used as a renewable fuel for the production of heat, power and cooling and different system are demonstrated or under development. Assuming a typical composition for a pyrolysis liquid (including 25wt% of water) the combustion can be written as:
C10H15O8 (l) + 9.75 O2 (g) = 10 CO2 (g) + 7.5 H2O (g) dH = 16.5 MJ/kg of pyrolysis liquid.
For the stoichiometric combustion of 1 kg of pyrolysis liquid about 6 Nm3 of air is needed, and 1.7 kg of CO2 is produced.
The production of heat and power can be further subdivided into:
The properties of fast pyrolysis liquids are very different from those of crude oil derived transportation fuels. Modification / upgrading is required to improve the compatibility with such fuels. As illustrated in the figure, various approaches are possible ranging from simple physical treatment to severe thermochemical chemical treatment.
Physical treatment and/or mild chemical treatment of pyrolysis liquid is meant to improve specific properties like acidity, viscosity and stability. It should simplify the application of the pyrolyis liquid in stationary engines and turbines. Examples of such treatments are blending emulsifying and esterification . It is important to note that they never enable automotive applications.
To produce real transportation fuels (diesel, kerosene, gasoline) from fast pyrolysis oil, a severe thermochemical treatment of the fast pyrolysis is needed (upgrading). It includes a full deoxygenation of the pyrolysis oil in a catalytic hydrotreatment process. Because full deoxygenation requires quite some hydrogen, an alternative approach is to just partially de-oxygenate the pyrolysis oil and finish the conversion to transportation fuel in an existing refinery unit crude oil refineries.
Research is ongoing  to investigate the various aspects relevant to the upgrading processes. It appears that two steps must be applied: a first one at 200 to 250 oC to stabilize the (very) reactive components in the oil, and a second one at 350 to 400 oC to deoxygenate the stabilized product in a further hydrotreating step. The presence of a proper catalyst in both steps is essential. Presumably carbohydrate chemistry is involved in the low temperature step, while lignin chemistry prevails at higher temperatures. The cellulose-derived fraction of the pyrolysis oil needs to be transformed first, preferably to alcohols, in a ‘mild hydrogenation’ step. Then, dehydration and hydrogenation can take place at more severe conditions. The high temperature step is more or less similar to petrochemical hydrotreatment. Full deoxygenation should be carried out while using active and selective catalysts to suppress charring, promote hydrogenation and reduce methanation. It may eventually result in carbon yields of above 50 wt.% (see diagram shown before). As an alternative to full deoxygenation of the pyrolysis oil in the catalytic hydrotreatment process, mixtures of transportation fuels can also be obtained by co-feeding partially upgraded fast pyrolysis oil to a FCC refinery unit. FCC. Petrobras (ref) has demonstrated that even co-feeding of crude pyrolysis oil is possible (in low quantities), but carbon yields will be lower then.
The proof of concept for feeding partially upgraded pyrolysis liquids to a FCC, was demonstrated first in the FP6 project BIOCOUP that was concluded in 2010. Currently (2016) the FP7 project FASTCARD is aiming at a more efficient conversion of biomass to biofuels by improving catalysts. It has been concluded already that ‘co-FCC of upgraded pyrolysis oil is technically possible. Regarding the FCC product spectrum, no unexpected deviations occur. It merely depends on the degree to which the pyrolysis oil has been upgraded and the co-feeding ratio. Typically, coke and gas yields are getting higher. Regarding the severity (pressure, temperature, space time) at which the pyrolysis liquids have been pre-processed in a prior hydrotreatment step, three types of pyrolysis derived feedstocks can be distinguished: (1) fully deoxygenated, (2) partially deoxygenated, and (3) untreated pyrolysis liquids. Fully deoxygenated liquids should behave similarly to the usual feed for FCC (VGO), while untreated pyrolysis liquids yield more coke and gas compared to VGO. Obviously, also the feed ratio of VGO over pyrolysis liquids will have a strong effect on the final result.
An indirect route to fuels and chemicals is via pyrolysis oil gasification. In a first step pyrolysis oil is gasified with steam and oxygen to a synthesis gas (CO/H2), whereafter this syngas can be converted catalytically to the desired product (e.g. Fischer Tropsch diesel). Pyrolysis oil gasification is technically well possible; Chemrec in Sweden, for instance, demonstrated the co-gasification of pyrolysis oil with black liquor successfully. Some advantages could be claimed for pyrolysis oil gasification if compared to solid biomass gasification. Firstly, pressurization of a liquid is far much easier than of a solid material. Pressurized gasification is always required when chemicals or fuels are to be synthesized. Secondly, the transport of a high-energy density liquid is much more efficient than of a voluminous biomass material. Since gasification for chemicals and fuels production requires large-scale processing, the collection of biomass would quickly become a limiting factor. Pyrolysis oil can be produced on a small scale at various biomass productions sites (decentralized) and easily collected / transported to a central large-scale gasification plant. Finally, a catalyst could be used in the gasification process, because the pyrolysis oil hardly contains any minerals capable of poisoning the catalyst. This "autothermal catalytic reforming" can then be carried out at significantly lower temperatures (cost benefit).
Chemicals and materials
Pyrolysis oil is a mixture of cracked components originating from the pyrolysis of the three main building blocks of biomass; cellulose, hemicellulose and lignine. Pyrolysis is a good pretreatment to facilitate the fractionation of biomass. After pyrolysis the (ash free) oil can easily be fractionated into three product streams namely; pyrolytic lignin (from lignin), pyrolytic sugars (from cellulose) and a watery phase containing smaller organic components e.g. acetic acid (mainly from hemicellulose). Pyrolysis oil as such or each of the fraction is considered to be a good renewable resource for renewable chemicals and materials.
The three fraction obtained from pyrolysis oil:
- Pyrolytic Lignin (~35% of the original carbon)
- Sugar Syrup (~45% of the original carbon)
- Aqueous phase (~20% of the original carbon)
Subsequently after fractionation of the pyrolysis oil, the obtained fractions can be further processed to produce chemicals and/or green products. A highly potential application for the pyrolytic lignin (looking at it's functionality) could be as a renewable substituent for fossil phenol in phenol/formaldehyde resins and derivatives. These types of resins are widely used in wood products like particle boards, plywood etc. recently it has already been demonstrated that the phenol in phenol/formaldehyde resins can be substituted up to 75 wt% by pyrolytic lignin standards for this type of (resin ).
Another interesting application of the pyrolytic lignin is in the replacement of fossil bitumen in various bitumen based materials e.g. in asphalt and roofing materials, the latter recently demonstrated in the Biotumen project. Also the pyrolytic lignin could be used in the production of green phenolic (mono-) derivatives, as a possible raw material for various coatings, composites and preservatives.
This sugar phase could be a renewable source for the production (via glucose) of e.g. bio-ethanol, levulinic acid, polyols etc. It has a high potential as a renewable sugar source due to the fact that it is not extracted from food sources like corn, sugarcane etc. Exploratory experiments by different researchers already indicated that a substantial amount of the pyrolytic sugars can be converted to fermentable sugar monomers (especially C6 sugars). Subsequently, fermentation of this phase by means of a yeast culture resulted in the production of ethanol.
From the last fraction, the water phase, which contains smaller volatile organics like VFA's a mixture of organic acid salts can be produced f.i. by means of a reaction with hydroxides or carbonates.
Almost all types of biomass are suitable for pyrolysis. Main requirements for the pyrolysis process is that the biomass is relatively dry (less than 10% moisture content) and a relatively small size (about 0.5 to 1 mm). Since few types of biomass meet these criteria when harvested commercial pyrolysis oil production plants require a biomass pretreatment section. This pretreatment section can be powered using the excess heat and power from the pyrolysis installation as long as the moisture content does not exceed a certain limit (55%.wt in the case of BTG-BTL's modified rotating cone technology).
Sustainability means that the needs of the present generation are met without compromising the ability of future generations to meet their own needs. The concept of sustainability is made tangible by definition of sustainability principles, criteria and measurable indicators. In case of biomass production and use the following themes are typically addressed: greenhouse gas savings, carbon stock change, land use change, biodiversity, emissions to soil, water and air, labour conditions, land use rights, and local economic impacts.
If bioliquids like pyrolysis liquid and biofuels like pyrolysis diesel are counted towards European renewable energy targets and/or receive renewable energy subsidies, they need to comply with a minimum set of sustainability criteria as defined in the Renewable Energy Directive (RED). Verification takes place by voluntary sustainability schemes that have been recognised by the European Commission, like NTA8080, ISCC, and RSB. These schemes have independent third party auditing procedures to verify that biomass is produced according to the sustainability criteria of these schemes and to trace the biomass troughout the supply chain. More information on certification of pyrolysis liquids can be found here.
The concept of biomass sustainability is still under development. For instance the issue of indirect land use change (ILUC) have been much debated on national and European level and resulted in a proposal of the European Commission to lower biofuels production from agricultural crops and to stimulate advanced biofuels.
Standards, Norms & Legislation
First standards on fast pyrolysis oil have been developed by ASTM . In 2014, the European standardization body CEN received a mandate to develop European standards and specifications for specific applications. Furthermore, to produce or import Fast Pyrolysis Liquid in the European Union a so-called REACH registration is required. REACH means Registration, Evaluation, Authorisation & restriction of Chemicals.
Transport of pyrolysis oil. Different transport modes can be considered like waterway, railway or tank container. Currently, commercial supply takes primarily place by tank container.
The development of this wiki or knowledge database was initiated as part of the Empyro project which is financially supported by the 7th Framework Programme of the European Commission (Grant number 239357). If you wish to contribute to this PyroWiki please send your credentials to the Administrator.
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