Pyrolysis

Pyrolysis is a thermal decomposition of materials

at elevated temperatures in an inert atmosphere
such as a vacuum gas.[1] It involves the change of
chemical composition and is irreversible. The
word is coined from the Greek-derived elements
pyro "fire" and lysis "separating".

Pyrolysis is most commonly applied to the

treatment of organic materials. It is one of the
processes involved in charring wood, starting at
200–300 °C (390–570 °F).[2] In general, pyrolysis
of organic substances produces volatile products
and leaves a solid residue enriched in carbon,
char. Extreme pyrolysis, which leaves mostly
carbon as the residue, is calledcarbonization.

Simplified depiction of pyrolysis chemistry

The process is used heavily in the chemical
industry, for example, to produce ethylene, many
forms of carbon, and other chemicals from
petroleum, coal, and even wood, to producecoke from coal. Aspirational applications of pyrolysis would convertbiomass into syngas
and biochar, waste plastics back into usable oil, or waste into safely disposable substances.

Contents
Process terminology and mechanism
Occurrence and uses
Ethylene
Coke, carbon, charcoals, and chars
Biofuels
Semiconductors
Recycling
Thermal cleaning
Fine chemical synthesis
History
See also
References
External links

Process terminology and mechanism

Certain uses of pyrolysis are called dry distillation, destructive distillation, or cracking. The processes involve thermal
depolymerization, i.e. the breaking of chemical bonds in macromolecules to give smaller fragments. The phenomenon involves
exceeding the ceiling temperature of polymers.
Pyrolysis differs from other processes likecombustion and hydrolysis in that it usually does not involve the addition of other reagents
such as oxygen (O2, in combustion) or water (in hydrolysis).[3] In practice, it is often not practical to achieve a completely O2- or
water-free conditions, especially as pyrolysis is often conducted on complex mixtures. The term has also been applied to the
decomposition of organic material in the presence of superheated water or steam (hydrous pyrolysis), for example, in the steam
cracking of oil. Pyrolysis has been assumed to take place during catagenesis, the conversion of buried organic matter to fossil fuels.
In vacuum pyrolysis, organic material is heated in a vacuum to decrease its boiling point and avoid adverse chemical reactions.
Called flash vacuum pyrolysis, this approach is used inorganic synthesis.

Pyrolysis can be analyzed by pyrolysis gas chromatography mass spectrometry (Py-GC-MS). In that technique, the volatile products
from pyrolysis are separated by gas chromatography, and identified by MS. The technique is applied to many aspects of pyrolysis
technology.[4][5] Pyrolysis is also used incarbon-14 dating.

Occurrence and uses

Ethylene
Pyrolysis is used to produce ethylene, the chemical compound produced on the largest scale industrially (>110 million tons/year in
2005). In this process, hydrocarbons from petroleum are heated to around 600 °C in the presence of steam, i.e. steam cracking. The
resulting ethylene is used to make antifreeze (ethylene glycol), PVC (via vinyl chloride), and many polymers, such as polyethylene
and polystyrene.[6]

Coke, carbon, charcoals, and chars

Carbon and carbon-rich materials have desirable properties but, are nonvolatile, even at high temperatures. Consequently, pyrolysis is
used to produce many kinds of carbon; these can be used for fuel, as reagents in steelmaking (coke), and as structural materials.

High temperature pyrolysis is used on a industrial scale to convert coal into coke for metallurgy, especially steelmaking. Volatile
products are often useful, including benzene and pyridine.[7] Coke can also be produced from the solid residue left from petroleum
refining.

The coke-making or "coking" process consists of heating the material

in "coking ovens" to very high temperatures (up to 900 °C or 1,700 °F)
so that those molecules are broken down into lighter volatile
substances, which leave the vessel, and a porous but hard residue that
is mostly carbon and inorganic ash. The amount of volatiles varies with
the source material, but is typically 25–30% of it by weight.

The original vascular structure of the wood and the pores created by
escaping gases combine to produce a light and porous material. By
starting with a dense wood-like material, such as nutshells or peach
stones, one obtains a form of charcoal with particularly fine pores (and
Typical organic products obtained by pyrolysis of
hence a much larger pore surface area), called activated carbon, which coal (X = CH, N).
is used as an adsorbent for a wide range of chemical substances.

Biochar is the residue of incomplete organic pyrolysis, e.g., from cooking fires. They are a key component of the terra preta soils
associated with ancient indigenous communities of the Amazon basin.[8] Terra preta is much sought by local farmers for its superior
fertility compared to the natural red soil of the region. Efforts are underway to recreate these soils through biochar, the solid residue
of pyrolysis of various materials, mostly organic waste.
Carbon fibers are filaments of carbon that can be used to make very strong yarns and textiles. Carbon fiber items are often produced
by spinning and weaving the desired item from fibers of a suitable polymer, and then pyrolyzing the material at a high temperature
(from 1,500–3,000 °C or 2,730–5,430 °F). The first carbon fibers were made from rayon, but polyacrylonitrile has become the most
common starting material. For their first workable electric lamps, Joseph Wilson Swan and Thomas Edison used carbon filaments
made by pyrolysis of cotton yarns and bamboo splinters, respectively.

Pyrolysis is the reaction used to coat a preformed substrate with a layer of pyrolytic carbon. This is typically done in a fluidized bed
reactor heated to 1,000–2,000 °C or 1,830–3,630 °F. Pyrolytic carbon coatings are used in many applications, including artificial
heart valves.[9]

Biofuels
Pyrolysis is the basis of several methods for producing fuel from biomass, i.e. lignocellulosic biomass.[10] Crops studied as biomass
feedstock for pyrolysis include native North American prairie grasses such as switchgrass and bred versions of other grasses such as
Miscantheus giganteus. Other sources of organic matter as feedstock for pyrolysis include greenwaste, sawdust, waste wood, nut
shells, straw, cotton trash, rice hulls. Animal waste including poultry litter, dairy manure, and potentially other manures are also
[11]
under evaluation. Some industrial byproducts are also suitable feedstock including paper sludge and distillers grain.

Synthetic diesel fuel by pyrolysis of organic materials is not yet economically competitive.[12] Higher efficiency is sometimes
achieved by flash pyrolysis, in which finely divided feedstock is quickly heated to between 350 and 500 °C (660 and 930 °F) for less
than 2 seconds.

The low quality of oils produced through pyrolysis can be improved by physical and chemical processes,[13] which might drive up
production costs, but may make sense economically as circumstances change.

There is also the possibility of integrating with other processes such as mechanical biological treatment and anaerobic digestion.[14]
[15] Fuel bio-oil can also be produced byhydrous pyrolysis.
Fast pyrolysis is also investigated for biomass conversions.

Semiconductors
The process of metalorganic vapour phase epitaxy (MOCVD) entails pyrolysis of volatile organometallic compounds to give
semiconductors, hard coatings, and other applicable materials. The reactions entail thermal degradation of precursors, with deposition
of the inorganic component and release of the hydrocarbons as gaseous waste. Since it is an atom-by-atom deposition, these atoms
organize themselves into crystals to form the bulksemiconductor. Silicon chips are produced by the pyrolysis of silane:

SiH4 → Si + 2 H2

Gallium arsenide, another semiconductor, forms upon co-pyrolysis oftrimethylgallium and arsine.

Recycling
Pyrolysis can also be used to treat plastic waste. The main advantage is the reduction in volume of the waste. In principle, pyrolysis
will regenerate the monomers (precursors) to the polymers that are treated, but in practice the process is neither clean nor
economically competitive source of monomers.[16][17][18]

In tire recycling, tire pyrolysis is well developed technology.[19] Other products from car tire pyrolysis include steel wires, carbon
black and bitumen.[20] The area faces legislative, economic, and marketing obstacles.[21] Oil derived from tire rubber pyrolysis
[22][23]
contains high sulfur content, which gives it high potential as a pollutant and should be desulfurized.

Thermal cleaning
Pyrolysis is also used for thermal cleaning, an industrial application
to remove organic substances such as polymers, plastics and coatings
from parts, products or production components like extruder screws,
spinnerets[24] and static mixers. During the thermal cleaning process,
at temperatures between 600 °F to 1000 °F (310 C° to 540 C°),[25]
organic material is converted by pyrolysis and oxidation into volatile
organic compounds, hydrocarbons and carbonized gas.[26] Inorganic
elements remain.[27]

Several types of thermal cleaning systems use pyrolysis:

Molten Salt Baths belong to the oldest thermal cleaning

systems; cleaning with amolten salt bath is very fast but
implies the risk of dangerous splatters, or other potential
hazards connected with the use of salt baths, like
explosions or highly toxichydrogen cyanide gas.[25]
Fluidized Bed Systems[28] use sand or aluminium oxide
as heating medium;[29] these systems also clean very fast Illustration of the MOCVD process, which entails
but the medium does not melt or boil, nor emit any vapors pyrolysis of volatile
or odors;[25] the cleaning process takes one to two
hours.[26]
Vacuum Ovens use pyrolysis in a vacuum[30] avoiding uncontrolled combustion inside the cleaning chamber; [25] the
[26]
cleaning process takes 8 to 30 hours. [31]

Burn-Off Ovens, also known as Heat-Cleaning Ovens, are gas-fired and used in the painting,coatings, electric
[32]
motors and plastics industries for removing organics from heavy and large metal parts.

Fine chemical synthesis

Pyrolysis is used in the production of chemical compounds, mainly
, but not only, in the research laboratory.

The area of boron-hydride clusters started with the study of the pyrolysis of diborane (B2H6) at ca. 200 °C. Products include the
clusters pentaborane and decaborane. These pyrolyses involve not only cracking (to give H [33]
2), but also recondensation.

The synthesis of nanoparticles,[34] zirconia[35] and oxides[36] utilizing an ultrasonic nozzle in a process called ultrasonic spray
pyrolysis (USP).

History
Pyrolysis has been used for turning wood intocharcoal since ancient times. Many important chemical substances, such as phosphorus
and sulfuric acid, were first obtained by this process. In their embalming process, the ancient Egyptians used methanol, which they
obtained from the pyrolysis of wood. The dry distillation of wood remained the major source of methanol into the early 20th
Century.[37]

See also
Karrick process Dextrin
Gasification Wood gas
Torrefaction Pyrolytic coating
Thermal decomposition

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External links
The dictionary definition ofpyrolysis at Wiktionary
In Situ Catalytic Fast Pyrolysis Technology Pathway National Renewable Energy Laboratory

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