Pyrolysis

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Burning pieces of wood, showing various stages of pyrolysis followed by oxidative combustion. Fire 1873.JPG
Burning pieces of wood, showing various stages of pyrolysis followed by oxidative combustion.

The pyrolysis (or devolatilization) process is the thermal decomposition of materials at elevated temperatures in an inert atmosphere. [1] It involves a change of chemical composition. The word is coined from the Greek-derived elements pyro "fire" and lysis "separating".

Contents

Pyrolysis is most commonly used in the treatment of organic materials. It is one of the processes involved in charring wood. [2] In general, pyrolysis of organic substances produces volatile products and leaves char, a carbon-rich, solid residue. Extreme pyrolysis, which leaves mostly carbon as the residue, is called carbonization. Pyrolysis is considered the first step in the processes of gasification or combustion. [3] [4]

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 produce coke from coal. It is used also in the conversion of natural gas (primarily methane) into non-polluting hydrogen gas and non-polluting solid carbon char, initiating production in industrial volume. [5] Aspirational applications of pyrolysis would convert biomass into syngas and biochar, waste plastics back into usable oil, or waste into safely disposable substances.

Terminology

Pyrolysis is one of the various types of chemical degradation processes that occur at higher temperatures (above the boiling point of water or other solvents). It differs from other processes like combustion and hydrolysis in that it usually does not involve the addition of other reagents such as oxygen (O2, in combustion) or water (in hydrolysis). [6] Pyrolysis produces solids (char), condensable liquids (tar), and uncondensing/permanent gasses. [7] [8] [9] [10]

Types of pyrolysis

Complete pyrolysis of organic matter usually leaves a solid residue that consists mostly of elemental carbon; the process is then called carbonization. More specific cases of pyrolysis include:

General processes and mechanisms

Processes in the thermal degradation of organic matter at atmospheric pressure. Processes in the thermal degredation of organic matter.svg
Processes in the thermal degradation of organic matter at atmospheric pressure.

Pyrolysis generally consists in heating the material above its decomposition temperature, breaking chemical bonds in its molecules. The fragments usually become smaller molecules, but may combine to produce residues with larger molecular mass, even amorphous covalent solids.

In many settings, some amounts of oxygen, water, or other substances may be present, so that combustion, hydrolysis, or other chemical processes may occur besides pyrolysis proper. Sometimes those chemicals are added intentionally, as in the burning of firewood, in the traditional manufacture of charcoal, and in the steam cracking of crude oil.

Conversely, the starting material may be heated in a vacuum or in an inert atmosphere to avoid chemical side reactions (such as combustion or hydrolysis). Pyrolysis in a vacuum also lowers the boiling point of the byproducts, improving their recovery.

When organic matter is heated at increasing temperatures in open containers, the following processes generally occur, in successive or overlapping stages:

Occurrence and uses

Cooking

Caramelisation of carrots.jpg
Caramelized onions are slightly pyrolyzed.
Verkohlte Pizza 2013-04-01-2658.jpg
This pizza is pyrolyzed, almost completely carbonized.

Pyrolysis has many applications in food preparation. [13] Caramelization is the pyrolysis of sugars in food (often after the sugars have been produced by the breakdown of polysaccharides). The food goes brown and changes flavour. The distinctive flavours are used in many dishes; for instance, caramelized onion is used in French onion soup. [14] [15] The temperatures needed for caramelization lie above the boiling point of water. [14] Frying oil can easily rise above boiling point. Putting a lid on the frying pan keeps the water in, and some of it re-condenses, keeping the temperature too cool to brown for longer.

Pyrolysis of food can also be undesirable, as in the charring of burnt food (at temperatures too low for the oxidative combustion of carbon to produce flames and burn the food to ash).

Coke, carbon, charcoals, and chars

Charcoal briquettes, often made from compressed sawdust or similar, in use.

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.

Charcoal is a less smoky fuel than pyrolyzed wood). [16] Some cities ban, or used to ban, wood fires; when residents only use charcoal (and similarly-treated rock coal, called coke) air pollution is significantly reduced. In cities where people do not generally cook or heat with fires, this is not needed. In the mid-20th century, "smokeless" legislation in Europe required cleaner-burning techniques, such as coke fuel [17] and smoke-burning incinerators [18] as an effective measure to reduce air pollution [17]

A blacksmith's forge, with a blower forcing air through a bed of fuel to raise the temperature of the fire. On the periphery, coal is pyrolyzed, absorbing heat; the coke at the center is almost pure carbon, and releases a lot of heat when the carbon oxidizes. Coal-forge-diagram.svg
A blacksmith's forge, with a blower forcing air through a bed of fuel to raise the temperature of the fire. On the periphery, coal is pyrolyzed, absorbing heat; the coke at the center is almost pure carbon, and releases a lot of heat when the carbon oxidizes.
Typical organic products obtained by pyrolysis of coal (X = CH, N). CoalPyrolysisProducts.png
Typical organic products obtained by pyrolysis of coal (X = CH, N).

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. High temperature pyrolysis is used on an industrial scale to convert coal into coke. This is useful in metallurgy, where the higher temperatures are necessary for many processes, such as steelmaking. Volatile by-products of this process are also often useful, including benzene and pyridine. [19] Coke can also be produced from the solid residue left from petroleum refining.

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 hence a much larger pore surface area), called activated carbon, which 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. [20] Terra preta is much sought by local farmers for its superior fertility and capacity to promote and retain an enhanced suite of beneficial microbiota, compared to the typical 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 produced by pyrolyzing a silk cocoon. Electron micrograph, scale bar at bottom left shows 100 mm. Carbon fibers from silk cocoon.tif
Carbon fibers produced by pyrolyzing a silk cocoon. Electron micrograph, scale bar at bottom left shows 100 μm.

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. [21]

Liquid and gaseous biofuels

Pyrolysis is the basis of several methods for producing fuel from biomass, i.e. lignocellulosic biomass. [22] 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, leaves, vegetables, nut shells, straw, cotton trash, rice hulls, and orange peels. [3] Animal waste including poultry litter, dairy manure, and potentially other manures are also under evaluation. Some industrial byproducts are also suitable feedstock including paper sludge, distillers grain, [23] and sewage sludge. [24]

In the biomass components, the pyrolysis of hemicellulose happens between 210 and 310 °C. [3] The pyrolysis of cellulose starts from 300-315 °C and ends at 360-380 °C, with a peak at 342-354 °C. [3] Lignin starts to decompose at about 200 °C and continues until 1000 °C. [25]

Synthetic diesel fuel by pyrolysis of organic materials is not yet economically competitive. [26] 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 two seconds.

Syngas is usually produced by pyrolysis. [13]

The low quality of oils produced through pyrolysis can be improved by physical and chemical processes, [27] 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. [28] Fast pyrolysis is also investigated for biomass conversions. [29] Fuel bio-oil can also be produced by hydrous pyrolysis.

Methane pyrolysis for hydrogen

Illustrating inputs and outputs of methane pyrolysis, an efficient one-step process to produce Hydrogen and no greenhouse gas Methane Pyrolysis-1.png
Illustrating inputs and outputs of methane pyrolysis, an efficient one-step process to produce Hydrogen and no greenhouse gas

Methane pyrolysis [30] is a non-polluting industrial process for hydrogen production from methane by removing solid carbon from natural gas. This one step process produces non-polluting hydrogen in high volume at low cost. Only water is released when hydrogen is used as the fuel for fuel-cell electric heavy truck transportation, [31] [32] [33] [34] [35] gas turbine electric power generation, [36] [37] and hydrogen for industrial processes including producing ammonia fertilizer and cement. [38] [39] Methane pyrolysis is the process operating around 1065 °C for producing hydrogen from natural gas that allows removal of carbon easily (solid non-polluting carbon is a byproduct of the process). [40] [41] The industrial quality solid carbon can then be sold or landfilled and is not released into the atmosphere, no emission of greenhouse gas (GHG), no ground water pollution in landfill. Volume production is being evaluated in the BASF "methane pyrolysis at scale" pilot plant, [42] the chemical engineering team at University of California - Santa Barbara [43] and in such research laboratories as Karlsruhe Liquid-metal Laboratory (KALLA). [44] Power for process heat consumed is only one seventh of the power consumed in the water electrolysis method for producing hydrogen. [45]

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 (1,112 °F) in the presence of steam; this is called steam cracking. The resulting ethylene is used to make antifreeze (ethylene glycol), PVC (via vinyl chloride), and many other polymers, such as polyethylene and polystyrene. [46]

Semiconductors

Illustration of the metalorganic vapour phase epitaxy process, which entails pyrolysis of volatiles MOCVDprocess.jpg
Illustration of the metalorganic vapour phase epitaxy process, which entails pyrolysis of volatiles

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 bulk semiconductor. Silicon chips are produced by the pyrolysis of silane:

SiH4 → Si + 2 H2.

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

Waste management

Pyrolysis can also be used to treat municipal solid waste and plastic waste. [4] [12] [47] 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 a clean nor an economically competitive source of monomers. [48] [49] [50]

In tire waste management, tire pyrolysis is well developed technology. [51] Other products from car tire pyrolysis include steel wires, carbon black and bitumen. [52] The area faces legislative, economic, and marketing obstacles. [53] Oil derived from tire rubber pyrolysis contains high sulfur content, which gives it high potential as a pollutant and should be desulfurized. [54] [55]

Alkaline pyrolysis of sewage sludge at low temperature of 500 °C can enhance H2 production with in-situ carbon capture. The use of NaOH as has the potential to produce H2-rich gas that can be used for fuels cells directly. [24] [56]

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 [57] and static mixers. During the thermal cleaning process, at temperatures between 310 C° to 540 C° (600 °F to 1000 °F), [58] organic material is converted by pyrolysis and oxidation into volatile organic compounds, hydrocarbons and carbonized gas. [59] Inorganic elements remain. [60]

Several types of thermal cleaning systems use pyrolysis:

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 H2), but also recondensation. [66]

The synthesis of nanoparticles, [67] zirconia [68] and oxides [69] utilizing an ultrasonic nozzle in a process called ultrasonic spray pyrolysis (USP).

Other uses and occurrences

PAHs generation

Polycyclic aromatic hydrocarbons (PAHs) can be generated from the pyrolysis of different solid waste fractions, [10] such as hemicellulose, cellulose, lignin, pectin, starch, polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), and polyethylene terephthalate (PET). PS, PVC, and lignin generate significant amount of PAHs. Naphthalene is the most abundant PAH among all the polycyclic aromatic hydrocarbons. [70]

When the temperature is increased from 500 to 900 °C, most PAHs increase. With the increase of the temperature, the percentage of light PAHs decrease and the percentage of heavy PAHs increase. [71] [72]

Study tools

Thermogravimetric analysis

Thermogravimetric analysis (TGA) is one of the most common techniques to investigate pyrolysis with no limitations of heat and mass transfer. The results can be used to determine mass loss kinetics. [3] [12] [4] [25] [47] Activation energies can be calculated using Kissinger method or peak analysis-least square method (PA-LSM). [4] [25]

TGA can couple with Fourier-transform infrared spectroscopy (FTIR) and mass spectrometry. As the increase of temperature, the volatiles generated from pyrolysis can be measured. [73] [56]

Macro-TGA

In TGA, sample is loaded first before the increase of temperature, and the heating rate is low (less than 100 °C min−1). Macro-TGA can use gram level samples which can be used to investigate the pyrolysis with mass and heat transfer effects. [4] [74]

Pyrolysis–gas chromatography–mass spectrometry

Pyrolysis mass spectrometry (Py-GC-MS) is an important laboratory procedure to determine the structure of compounds. [75] [76]

History

Oak charcoal JapaneseOakCharcoal KuroSumi.jpg
Oak charcoal

Pyrolysis has been used for turning wood into charcoal since ancient times. 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. [77]

Pyrolysis was instrumental in the discovery of many important chemical substances, such as phosphorus (from ammonium sodium hydrogen phosphate NH
4
NaHPO
4
in concentrated urine) and oxygen (from mercuric oxide and various nitrates).

See also

Related Research Articles

Biogas Gases produced by decomposing organic matter

Biogas is a mixture of gases, primarily consisting of methane and carbon dioxide, produced from raw materials such as agricultural waste, manure, municipal waste, plant material, sewage, green waste or food waste. It is a renewable energy source.

Syngas Fossil fuel derived from other hydrocarbon sources

Syngas, or synthesis gas, is a fuel gas mixture consisting primarily of hydrogen, carbon monoxide, and very often some carbon dioxide. The name comes from its use as intermediates in creating synthetic natural gas (SNG) and for producing ammonia or methanol. Syngas is usually a product of coal gasification and the main application is electricity generation. Syngas is combustible and can be used as a fuel of internal combustion engines. Historically, it has been used as a replacement for gasoline, when gasoline supply has been limited; for example, wood gas was used to power cars in Europe during WWII. However, it has less than half the energy density of natural gas.

Waste management Activities and actions required to manage waste from its source to its final disposal

Waste management includes the processes and actions required to manage waste from its inception to its final disposal. This includes the collection, transport, treatment and disposal of waste, together with monitoring and regulation of the waste management process and waste-related laws, technologies, economic mechanisms.

Gasification Form of energy conversion

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 (CO
2
). This is achieved by reacting the feedstock material at high temperatures (typically >700 °C), without combustion, via controlling the amount of oxygen and/or steam present in the reaction. The resulting gas mixture is called syngas (from synthesis gas) or producer gas and is itself a fuel due to the flammability of the H2 and CO of which the gas is largely composed. Power can be derived from the subsequent combustion of the resultant gas, and is considered to be a source of renewable energy if the gasified compounds were obtained from biomass feedstock.

Solid fuel

Solid fuel refers to various forms of solid material that can be burnt to release energy, providing heat and light through the process of combustion. Solid fuels can be contrasted with liquid fuels and gaseous fuels. Common examples of solid fuels include wood, charcoal, peat, coal, hexamine fuel tablets, dry dung, wood pellets, corn, wheat, rye, and other grains. Solid fuels are extensively used in rocketry as solid propellants. Solid fuels have been used throughout human history to create fire and solid fuel is still in widespread use throughout the world in the present day.

The Fischer–Tropsch process is a collection of chemical reactions that converts a mixture of carbon monoxide and hydrogen or water gas into liquid hydrocarbons. These reactions occur in the presence of metal catalysts, typically at temperatures of 150–300 °C (302–572 °F) and pressures of one to several tens of atmospheres. The process was first developed by Franz Fischer and Hans Tropsch at the Kaiser-Wilhelm-Institut für Kohlenforschung in Mülheim an der Ruhr, Germany, in 1925.

Steam reforming or steam methane reforming is a method for producing syngas (hydrogen and carbon monoxide) by reaction of hydrocarbons with water. Commonly natural gas is the feedstock. The main purpose of this technology is hydrogen production. The reaction is represented by this equilibrium:

Anaerobic digestion Processes by which microorganisms break down biodegradable material in the absence of oxygen

Anaerobic digestion is a sequence of processes by which microorganisms break down biodegradable material in the absence of oxygen. The process is used for industrial or domestic purposes to manage waste or to produce fuels. Much of the fermentation used industrially to produce food and drink products, as well as home fermentation, uses anaerobic digestion.

Synthetic fuel 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 reforming of natural gas

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 reforming of natural gas.

Biomass to liquid is a multi-step process of producing synthetic hydrocarbon fuels made from biomass via a thermochemical route.

Renewable Natural Gas (RNG), also known as Sustainable Natural Gas (SNG) or biomethane, is a biogas which has been upgraded to a quality similar to fossil natural gas and having a methane concentration of 90% or greater. By upgrading the quality of methane-based biogas to that of natural gas, it becomes possible to distribute the gas to customers via the existing gas grid within existing appliances. Renewable natural gas is a subset of synthetic natural gas or substitute natural gas (SNG).

Waste-to-energy

Waste-to-energy (WtE) or energy-from-waste (EfW) is the process of generating energy in the form of electricity and/or heat from the primary treatment of waste, or the processing of waste into a fuel source. WtE is a form of energy recovery. Most WtE processes generate electricity and/or heat directly through combustion, or produce a combustible fuel commodity, such as methane, methanol, ethanol or synthetic fuels.

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 500 °C with subsequent cooling. Pyrolysis oil is a kind of tar and normally contains levels of oxygen too high to be considered a pure hydrocarbon. This high oxygen content results in non-volatility, corrosiveness, immiscibility with fossil fuels, thermal instability, and a tendency to polymerize 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.

Hydrogen production is the family of industrial methods for generating hydrogen gas. As of 2020, the majority of hydrogen (∼95%) is produced from fossil fuels by steam reforming of natural gas, partial oxidation of methane, and coal gasification. Other methods of hydrogen production include biomass gasification, no CO2 emissions methane pyrolysis, and electrolysis of water. The latter processes, methane pyrolysis as well as water electrolysis can be done directly with any source of electricity, such as solar power.

Plasma gasification is an extreme thermal process using plasma which converts organic matter into a syngas which is primarily made up of hydrogen and carbon monoxide. A plasma torch powered by an electric arc is used to ionize gas and catalyze organic matter into syngas, with slag remaining as a byproduct. It is used commercially as a form of waste treatment and has been tested for the gasification of refuse-derived fuel, biomass, industrial waste, hazardous waste, and solid hydrocarbons, such as coal, oil sands, petcoke and oil shale.

Biochar Lightweight black residue, made of carbon and ashes, after pyrolysis of biomass

Biochar is charcoal that is produced by pyrolysis of biomass in the absence of oxygen; it is used as a soil amendment. Biochar is defined by the International Biochar Initiative as "The solid material obtained from the thermochemical conversion of biomass in an oxygen-limited environment". Biochar is a stable solid that is rich in carbon and can endure in soil for thousands of years.

Second-generation biofuels, also known as advanced biofuels, are fuels that can be manufactured from various types of non-food biomass. Biomass in this context means plant materials and animal waste used especially as a source of fuel.

Reactive flash volatilization (RFV) is a chemical process that rapidly converts nonvolatile solids and liquids to volatile compounds by thermal decomposition for integration with catalytic chemistries.

Staged reforming is a thermochemical process to convert organic material or bio waste such as wood, dung or hay into combustible gases containing methane, carbon monoxide and hydrogen. The single-stage reforming of bio materials results in high dust and tar yields in the produced gas restricting its use, hence the use of staged reforming. After reforming the output is approximately 80% fuel gas and 20% cokes.

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 heating value of 33.8-36.9 MJ/kg and 5-20 wt% oxygen and renewable chemicals.

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