Pyrolysis oil, sometimes also known as bio-crude or bio-oil, is a

synthetic fuel Synthetic fuel or synfuel is a liquid fuel, or sometimes gaseous fuel, obtained from syngas, a mixture of carbon monoxide and hydrogen, in which the syngas was derived from gasification of solid feedstocks such as coal or biomass or by refo ...

under investigation as substitute for

petroleum Petroleum, also known as crude oil, or simply oil, is a naturally occurring yellowish-black liquid mixture of mainly hydrocarbons, and is found in geological formations. The name ''petroleum'' covers both naturally occurring unprocessed crud ...

. It is obtained by heating dried

biomass Biomass is plant-based material used as a fuel for heat or electricity production. It can be in the form of wood, wood residues, energy crops, agricultural residues, and waste from industry, farms, and households. Some people use the terms bio ...

without

oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements ...

in a reactor at a temperature of about with subsequent cooling. Pyrolysis oil is a kind of

tar Tar is a dark brown or black viscous liquid of hydrocarbons and free carbon, obtained from a wide variety of organic materials through destructive distillation. Tar can be produced from coal, wood, petroleum, or peat. "a dark brown or black bi ...

and normally contains levels of oxygen too high to be considered a pure

hydrocarbon In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and hydrophobic, and their odors are usually weak or ...

. This high oxygen content results in non-volatility, corrosiveness, immiscibility with fossil fuels, thermal instability, and a tendency to

polymerize In polymer chemistry, polymerization (American English), or polymerisation (British English), is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are many for ...

when exposed to air. As such, it is distinctly different from petroleum products. Removing oxygen from bio-oil or nitrogen from algal bio-oil is known as upgrading.

Standards

There are few standards for pyrolysis oil because of limited efforts to produce it. One of the few standards is from

ASTM ASTM International, formerly known as American Society for Testing and Materials, is an international standards organization that develops and publishes voluntary consensus technical standards for a wide range of materials, products, systems, an ...

Feedstock decomposition

Pyrolysis The pyrolysis (or devolatilization) process is the thermal decomposition of materials at elevated temperatures, often in an inert atmosphere. It involves a change of chemical composition. The word is coined from the Greek-derived elements '' ...

is a well established technique for

decomposition Decomposition or rot is the process by which dead organic substances are broken down into simpler organic or inorganic matter such as carbon dioxide, water, simple sugars and mineral salts. The process is a part of the nutrient cycle and ...

organic material Organic matter, organic material, or natural organic matter refers to the large source of carbon-based compounds found within natural and engineered, terrestrial, and aquatic environments. It is matter composed of organic compounds that have c ...

at elevated temperatures in the absence of

into oil and other constituents. In second-generation biofuel applications—forest and agricultural residues, waste wood, yard waste, and energy crops can be used as feedstock.

Wood Pyrolysis

When wood is heated above it begins a process of decomposition called

carbonization Carbonization is the conversion of organic matters like plants and dead animal remains into carbon through destructive distillation. Complexity in carbonization Carbonization is a pyrolytic reaction, therefore, is considered a complex proces ...

. In the absence of oxygen, the final product is

charcoal Charcoal is a lightweight black carbon residue produced by strongly heating wood (or other animal and plant materials) in minimal oxygen to remove all water and volatile constituents. In the traditional version of this pyrolysis process, ...

. If sufficient oxygen is present, the wood will burn when it reaches a temperature of about leaving

wood ash Wood ash is the powdery residue remaining after the combustion of wood, such as burning wood in a fireplace, bonfire, or an industrial power plant. It is largely composed of calcium compounds along with other non-combustible trace elements presen ...

behind. If wood is heated away from air, the moisture is first driven off and until this is complete, the wood temperature remains at about . When the wood is dry its temperature rises, and at about it begins to spontaneously decompose and generate heat. This is the well known exothermic reaction which takes place in the burning of charcoal. At this stage evolution of carbonization by-products starts. These substances are given off gradually as the temperature rises and at about the evolution is complete. The solid residue, charcoal, is mainly carbon (about 70%), with the remainder being tar-like substances which can be driven off or decomposed completely only by raising the temperature to above about 600 °C to produce

Biochar Biochar is the lightweight black residue, made of carbon and ashes, remaining after the pyrolysis of biomass. Biochar is defined by the International Biochar Initiative as "the solid material obtained from the thermochemical conversion of ...

, a high-carbon, fine-grained residue that today is produced through modern

pyrolysis The pyrolysis (or devolatilization) process is the thermal decomposition of materials at elevated temperatures, often in an inert atmosphere. It involves a change of chemical composition. The word is coined from the Greek-derived elements '' ...

processes, which is the direct

thermal decomposition Thermal decomposition, or thermolysis, is a chemical decomposition caused by heat. The decomposition temperature of a substance is the temperature at which the substance chemically decomposes. The reaction is usually endothermic as heat is re ...

of biomass in the absence of

, which prevents

combustion Combustion, or burning, is a high-temperature exothermic redox chemical reaction between a fuel (the reductant) and an oxidant, usually atmospheric oxygen, that produces oxidized, often gaseous products, in a mixture termed as smoke. Combus ...

, to obtain an array of solid (biochar), liquid—Pyrolysis oil (bio-oil/pyrolysis-oil), and gas (

syngas Syngas, or synthesis gas, is a mixture of hydrogen and carbon monoxide, in various ratios. The gas often contains some carbon dioxide and methane. It is principly used for producing ammonia or methanol. Syngas is combustible and can be used as ...

) products. The specific yield from the pyrolysis is dependent on process conditions. such as temperature, and can be optimized to produce either energy or biochar. Temperatures of produce more

char Char may refer to: People * Char Fontane, American actress * Char Margolis, American spiritualist * René Char (1907–1988), French poet *The Char family of Colombia: ** Fuad Char, Colombian senator ** Alejandro Char Chaljub, mayor of Barranquill ...

, while temperatures above favor the yield of liquid and gaseous fuel components. (See Table 1 for differences in output for Fast, Intermediate, Slow, and Gasification). Pyrolysis occurs more quickly at higher temperatures, typically requiring seconds instead of hours. High temperature pyrolysis is also known as

gasification Gasification is a process that converts biomass- or fossil fuel-based carbonaceous materials into gases, including as the largest fractions: nitrogen (N2), carbon monoxide (CO), hydrogen (H2), and carbon dioxide (). This is achieved by reacting ...

, and produces primarily

. Typical yields are 60%

bio-oil Pyrolysis oil, sometimes also known as bio-crude or bio-oil, is a synthetic fuel under investigation as substitute for petroleum. It is obtained by heating dried biomass without oxygen in a reactor at a temperature of about with subsequent co ...

, 20% biochar, and 20% syngas. By comparison, slow pyrolysis can produce substantially more char (~50%). For typical inputs, the energy required to run a “fast” pyrolyzer is approximately 15% of the energy that it outputs. Modern pyrolysis plants can use the syngas created by the pyrolysis process and output 3–9 times the amount of energy required to run.

Algal Pyrolysis

Algae may be subjected to high temperatures (~500 °C) and normal atmospheric pressures. The resultant products include oil and nutrients such as nitrogen, phosphorus, and potassium.

There are numerous papers on the pyrolysis of lignocellulosic biomass. However, very few reports are available for algal bio-oil production via pyrolysis. Miao et al. (2004b) performed fast pyrolysis of Chllorella protothecoides and Microcystis areuginosa at 500 °C, and bio-oil yields of 18% and 24% were obtained, respectively. The bio-oil exhibited a higher carbon and nitrogen content, lower oxygen content than wood bio-oil. When Chllorella protothecoides was cultivated heterotrophically, bio-oil yield increased to 57.9% with a heating value of 41 MJ/kg (Miao et al., 2004a). Recently when microalgae become a hot research topic as the third generation of biofuel, pyrolysis has drawn more attention as a potential conversion method for algal biofuel production. Pan et al. (2010) investigated slow pyrolysis of Nannochloropsis sp. residue with and without the presence of HZSM-5 catalyst and obtained bio-oil rich in aromatic hydrocarbons from catalytic pyrolysis. Algal pyrolytic liquids separate into two phases with the top phase called bio-oil (Campanella et al., 2012; Jena et al., 2011a). The higher heating values (HHV) of algal bio-oil are in the range of 31−36 MJ/kg, generally higher than those of lignocellulosic feedstocks. Pyrolytic bio-oil consists of compounds with lower mean molecular weights and contains more low boiling compounds than bio-oil produced by hydrothermal liquefaction. These properties are similar to those of Illinois shale oil (Jena et al., 2011a; Vardon et al., 2012), which may indicate that pyrolytic bio-oil is suited for replacing petroleum. In addition, the high protein content in microalgae led to a high N content in the bio-oil, resulting in undesirable NOx emissions during combustion and deactivation of acidic catalysts when co-processed in existing 10 crude oil refineries. Algal bio-oil had better qualities in many aspects than those produced from lignocellulosic biomass. For example, algal bio-oil has a higher heating value, a lower oxygen content and a greater than 7 pH value. However, upgrading towards the removal of nitrogen and oxygen in the bio-oil is still necessary before it can be used as drop-in fuels.

Algal Hydrothermal Liquefaction

Hydrothermal liquefaction Hydrothermal liquefaction (HTL) is a thermal depolymerization process used to convert wet biomass, and other macromolecules, into crude-like oil under moderate temperature and high pressure. The crude-like oil has high energy density with a lower ...

(HTL) is a

thermal depolymerization Thermal depolymerization (TDP) is the process of converting a polymer into a monomer or a mixture of monomers, by predominantly thermal means. It may be catalysed or un-catalysed and is distinct from other forms of depolymerisation which may rely o ...

process used to convert wet

into an oil—sometimes referred to as bio-oil or bio-crude—under a moderate temperature and high pressure of 350 °C (662 °F) and 3,000 pounds per square inch (21,000 kPa). The crude-like oil (or bio-oil) has high energy density with a

lower heating value The heating value (or energy value or calorific value) of a substance, usually a fuel or food (see food energy), is the amount of heat released during the combustion of a specified amount of it. The ''calorific value'' is the total energy rele ...

of 33.8-36.9 MJ/kg and 5-20 wt% oxygen and renewable chemicals. The HTL process differs from

as it can process wet biomass and produce a bio-oil that contains approximately twice the energy density of pyrolysis oil. Pyrolysis is a related process to HTL, but biomass must be processed and dried in order to increase the yield. The presence of water in pyrolysis drastically increases the heat of vaporization of the organic material, increasing the energy required to decompose the biomass. Typical pyrolysis processes require a water content of less than 40% to suitably convert the biomass to bio-oil. This requires considerable pretreatment of wet biomass such as tropical grasses, which contain a water content as high as 80-85%, and even further treatment for aquatic species, which can contain higher than 90% water content. Per Algal HTL, the properties of the resulting bio-oil are affected by temperature, reaction time, algae species, algae concentration, reaction atmosphere, and catalysts, in subcritical water reaction conditions.

Bio-crude

Bio-oil typically requires significant additional treatment to render it suitable as a refinery feedstock to replace crude oil derived from

coal-oil Coal oil is a shale oil obtained from the destructive distillation of cannel coal, mineral wax, or bituminous shale, once used widely for illumination. Chemically similar to the more refined, petroleum-derived kerosene, it consists mainly of sev ...

, or

coal-tar Coal tar is a thick dark liquid which is a by-product of the production of coke and coal gas from coal. It is a type of creosote. It has both medical and industrial uses. Medicinally it is a topical medication applied to skin to treat psoriasis ...

Tar Tar is a dark brown or black viscous liquid of hydrocarbons and free carbon, obtained from a wide variety of organic materials through destructive distillation. Tar can be produced from coal, wood, petroleum, or peat. "a dark brown or black bi ...

is a black mixture of

hydrocarbons In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and hydrophobic, and their odors are usually weak or ...

and free

carbon Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent—its atom making four electrons available to form covalent chemical bonds. It belongs to group 14 of the periodic table. Carbon ma ...

obtained from a wide variety of

s through

destructive distillation Destruction may refer to: Concepts * Destruktion, a term from the philosophy of Martin Heidegger * Destructive narcissism, a pathological form of narcissism * Self-destructive behaviour, a widely used phrase that ''conceptualises'' certain kind ...

. Tar can be produced from

coal Coal is a combustible black or brownish-black sedimentary rock, formed as rock strata called coal seams. Coal is mostly carbon with variable amounts of other elements, chiefly hydrogen, sulfur, oxygen, and nitrogen. Coal is formed when ...

wood Wood is a porous and fibrous structural tissue found in the stems and roots of trees and other woody plants. It is an organic materiala natural composite of cellulose fibers that are strong in tension and embedded in a matrix of lignin ...

, or

peat Peat (), also known as turf (), is an accumulation of partially Decomposition, decayed vegetation or organic matter. It is unique to natural areas called peatlands, bogs, mires, Moorland, moors, or muskegs. The peatland ecosystem covers and ...

. *

Pine tar Pine tar is a form of wood tar produced by the high temperature carbonization of pine wood in anoxic conditions (dry distillation or destructive distillation). The wood is rapidly decomposed by applying heat and pressure in a closed container; ...

is a sticky material produced by the high temperature carbonization of

pine A pine is any conifer tree or shrub in the genus ''Pinus'' () of the family (biology), family Pinaceae. ''Pinus'' is the sole genus in the subfamily Pinoideae. The World Flora Online created by the Royal Botanic Gardens, Kew and Missouri Botanic ...

wood in

anoxic The term anoxia means a total depletion in the level of oxygen, an extreme form of hypoxia or "low oxygen". The terms anoxia and hypoxia are used in various contexts: * Anoxic waters, sea water, fresh water or groundwater that are depleted of diss ...

conditions (dry distillation or

). The wood is rapidly decomposed by applying heat and pressure in a closed container; the primary resulting products are

and pine

. Pine tar consists primarily of

aromatic hydrocarbons Aromatic compounds, also known as "mono- and polycyclic aromatic hydrocarbons", are organic compounds containing one or more aromatic rings. The parent member of aromatic compounds is benzene. The word "aromatic" originates from the past groupin ...

, tar acids and tar bases. Components of tar vary according to the

pyrolytic The pyrolysis (or devolatilization) process is the thermal decomposition of materials at elevated temperatures, often in an inert atmosphere. It involves a change of chemical composition. The word is coined from the Greek-derived elements ''pyr ...

process (e.g. method, duration, temperature) and origin of the wood (e.g. age of pine trees, type of soil and moisture conditions during tree growth). * Birch tar is a substance (liquid when heated) derived from the

dry distillation Dry distillation is the heating of solid materials to produce gaseous products (which may condense into liquids or solids). The method may involve pyrolysis or thermolysis, or it may not (for instance, a simple mixture of ice and glass could be s ...

of the bark of the

birch A birch is a thin-leaved deciduous hardwood tree of the genus ''Betula'' (), in the family Betulaceae, which also includes alders, hazels, and hornbeams. It is closely related to the beech- oak family Fagaceae. The genus ''Betula'' cont ...

tree. It is compounded of

phenols In organic chemistry, phenols, sometimes called phenolics, are a class of chemical compounds consisting of one or more hydroxyl groups (— O H) bonded directly to an aromatic hydrocarbon group. The simplest is phenol, . Phenolic compounds are ...

such as

guaiacol Guaiacol () is an organic compound with the formula C6H4(OH)(OCH3). It is a phenolic compound containing an methoxy functional group. Guaiacol appears as a viscous colorless oil, although aged or impure samples are often yellowish. It occurs wid ...

cresol Cresols (also hydroxytoluene or cresylic acid) are a group of aromatic organic compounds. They are widely-occurring phenols (sometimes called ''phenolics'') which may be either natural or manufactured. They are also categorized as methylphenol ...

, xylenol and creosol (not to be confused with

). Wood-tar

creosote Creosote is a category of carbonaceous chemicals formed by the distillation of various tars and pyrolysis of plant-derived material, such as wood or fossil fuel. They are typically used as preservatives or antiseptics. Some creosote types were ...

is a colourless to yellowish greasy liquid with a smoky odor, produces a sooty flame when burned, and has a burned taste. It is non-buoyant in water, with a

specific gravity Relative density, or specific gravity, is the ratio of the density (mass of a unit volume) of a substance to the density of a given reference material. Specific gravity for liquids is nearly always measured with respect to water at its dens ...

of 1.037 to 1.087, retains fluidity at a very low temperature, and boils at 205-225 °C. When transparent, it is in its purest form. Dissolution in water requires up to 200 times the amount of water as the base creosote. The creosote is a combination of natural

: primarily

and creosol (4-methylguaiacol), which will typically constitute 50% of the oil; second in prevalence,

and xylenol; the rest being a combination of monophenols and

polyphenol Polyphenols () are a large family of naturally occurring organic compounds characterized by multiples of phenol units. They are abundant in plants and structurally diverse. Polyphenols include flavonoids, tannic acid, and ellagitannin, some ...

s. Pitch is a name for any of a number of

viscoelastic In materials science and continuum mechanics, viscoelasticity is the property of materials that exhibit both viscous and elastic characteristics when undergoing deformation. Viscous materials, like water, resist shear flow and strain linearly ...

polymer A polymer (; Greek '' poly-'', "many" + '' -mer'', "part") is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...

s. Pitch can be natural or manufactured, derived from

coal tar Coal tar is a thick dark liquid which is a by-product of the production of coke and coal gas from coal. It is a type of creosote. It has both medical and industrial uses. Medicinally it is a topical medication applied to skin to treat pso ...

or plants.

Black liquor In industrial chemistry, black liquor is the by-product from the kraft process when digesting pulpwood into paper pulp removing lignin, hemicelluloses and other extractives from the wood to free the cellulose fibers. The equivalent material i ...

and Tall oil is a viscous liquid by-product of wood pulp manufacturing. Rubber oil is the product of the pyrolysis method for recycling used tires.

Biofuel

Biofuel Biofuel is a fuel that is produced over a short time span from biomass, rather than by the very slow natural processes involved in the formation of fossil fuels, such as oil. According to the United States Energy Information Administration ...

s are synthesized from intermediary products such as syngas using methods that are identical in processes involving conventional feedstocks, first generation and second generation biofuels. The distinguishing feature is the technology involved in producing the intermediary product, rather than the ultimate off-take. A

Biorefinery A biorefinery is a refinery that converts biomass to energy and other beneficial byproducts (such as chemicals). The International Energy Agency Bioenergy Task 42 defined biorefining as "the sustainable processing of biomass into a spectrum of bio ...

is a facility that integrates biomass conversion processes and equipment to produce fuels, power, heat, and value-added chemicals from

. The biorefinery concept is analogous to today's

petroleum refinery An oil refinery or petroleum refinery is an industrial process plant where petroleum (crude oil) is transformed and refined into useful products such as gasoline (petrol), diesel fuel, asphalt base, fuel oils, heating oil, kerosene, liquefie ...

, which produce multiple fuels and products from

. *

Biodiesel Biodiesel is a form of diesel fuel derived from plants or animals and consisting of long-chain fatty acid esters. It is typically made by chemically reacting lipids such as animal fat ( tallow), soybean oil, or some other vegetable oi ...

is a diesel fuel derived from animal or plant lipids (oils and fats). A variety of oils can be used as biodiesel

feedstock A raw material, also known as a feedstock, unprocessed material, or primary commodity, is a basic material that is used to produce goods, finished goods, energy, or intermediate materials that are feedstock for future finished products. As feeds ...

. *

Wood diesel Wood diesel is a new biofuel developed by the University of Georgia from woodchips. In the process, oil is extracted and then added to unmodified diesel engines. In the process, either new plants are grown to be used in the process, or a new crop ...

. A new biofuel was developed by the

University of Georgia , mottoeng = "To teach, to serve, and to inquire into the nature of things.""To serve" was later added to the motto without changing the seal; the Latin motto directly translates as "To teach and to inquire into the nature of things." , establ ...

from

woodchips Woodchips are small- to medium-sized pieces of wood formed by cutting or chipping larger pieces of wood such as trees, branches, logging residues, stumps, roots, and wood waste. Woodchips may be used as a biomass solid fuel and are raw materia ...

. The oil is extracted and then added to unmodified diesel engines. Either new plants are used or planted to replace the old plants. The charcoal byproduct is put back into the soil as a fertilizer. This biofuel can actually be carbon negative not just carbon neutral. Carbon negative processes decrease carbon dioxide in the air reversing the

greenhouse effect The greenhouse effect is a process that occurs when energy from a planet's host star goes through the planet's atmosphere and heats the planet's surface, but greenhouse gases in the atmosphere prevent some of the heat from returning directly ...

not just reducing it. *

Algae fuel Algae fuel, algal biofuel, or algal oil is an alternative to liquid fossil fuels that uses algae as its source of energy-rich oils. Also, algae fuels are an alternative to commonly known biofuel sources, such as corn and sugarcane. When made fr ...

s, can be produced from various types of

algae Algae (; singular alga ) is an informal term for a large and diverse group of photosynthetic eukaryotic organisms. It is a polyphyletic grouping that includes species from multiple distinct clades. Included organisms range from unicellular micr ...

, and are dependent on the technique and the part of the cells used, some species of algae can produce 50% or more of their dry weight in the form of oil. The

lipid Lipids are a broad group of naturally-occurring molecules which includes fats, waxes, sterols, fat-soluble vitamins (such as vitamins A, D, E and K), monoglycerides, diglycerides, phospholipids, and others. The functions of lipids in ...

, or oily part of the algae biomass can be extracted and converted into biodiesel through a process similar to that used for any other vegetable oil, or converted in a refinery into "drop-in" replacements for petroleum-based fuels.

Algaculture Algaculture is a form of aquaculture involving the farming of species of algae. The majority of algae that are intentionally cultivated fall into the category of microalgae (also referred to as phytoplankton, microphytes, or planktonic algae). Mac ...

can use waste materials such as sewage and without displacing land currently used for food production.

References

{{Reflist

External links

Pyrolysis Oil: An Innovative Liquid Biofuel for Heating

PyroKnown
website is dedicated to sharing knowledge and learning about biomass fast pyrolysis.

* ttp://www.nrel.gov/docs/fy07osti/37779.pdf Large-Scale Pyrolysis Oil Production: A Technology Assessment and Economic Analysis Synthetic fuels Biofuels Pyrolysis