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Monday, April 14, 2025

Pyrolysis

From Wikipedia, the free encyclopedia
https://en.wikipedia.org/wiki/Pyrolysis
Burning pieces of wood, showing various stages of pyrolysis followed by oxidative combustion.

Pyrolysis is a process involving the separation of covalent bonds in organic matter by thermal decomposition within an inert environment without oxygen.

Etymology

The word pyrolysis is coined from the Greek-derived elements pyro- (from Ancient Greek πῦρ : pûr - "fire, heat, fever") and lysis (λύσις : lúsis - "separation, loosening").

Applications

Pyrolysis is most commonly used in the treatment of organic materials. It is one of the processes involved in the charring of wood[4] or pyrolysis of biomass. 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 one of the steps in the processes of gasification or combustion. Laypeople often confuse pyrolysis gas with syngas. Pyrolysis gas has a high percentage of heavy tar fractions, which condense at relatively high temperatures, preventing its direct use in gas burners and internal combustion engines, unlike syngas.

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, or to produce coke from coal. It is used also in the conversion of natural gas (primarily methane) into hydrogen gas and solid carbon char, recently introduced on an industrial scale. 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 (O
2
, in combustion) or water (in hydrolysis). Pyrolysis produces solids (char), condensable liquids, (light and heavy oils and tar), and non-condensable gasses.

Pyrolysis is different from gasification. In the chemical process industry, pyrolysis refers to a partial thermal degradation of carbonaceous materials that takes place in an inert (oxygen free) atmosphere and produces both gases, liquids and solids. The pyrolysis can be extended to full gasification that produces mainly gaseous output, often with the addition of e.g. water steam to gasify residual carbonic solids, see Steam reforming.

Types

Specific types of pyrolysis include:


Other pyrolysis types come from a different classification that focuses on the pyrolysis operating conditions and heating system used, which have an impact on the yield of the pyrolysis products.

Pyrolysis Operating conditions Pyrolysis product yield (wt%)
Slow low temperature pyrolysis Temperature: 250-450 °C

Vapor residence time: 10-100 min

Heating rate: 0.1-1 °C/s

Feedstock size: 5-50 mm

Bio-oil ~30

Biochar~35

Gases~35

Intermediate pyrolysis Temperature: 600-800 °C

Vapor residence time: 0.5-20 s

Heating rate: 1.0-10 °C/s

Feedstock size: 1-5 mm

Bio-oil~50

Biochar~25

Gases~35

Fast low temperature pyrolysis Temperature: 250-450°C

Vapor residence time: 0.5-5 s

Heating rate: 10-200 °C/s

Feedstock size: <3 mm

Bio-oil ~50

Biochar~20

Gases~30

Flash pyrolysis Temperature: 800-1000 °C

Vapor residence time: <5 s

Heating rate: >1000 °C/s

Feedstock size: <0.2 mm

Bio-oil ~75

Biochar~12

Gases~13

Hydro pyrolysis Temperature: 350-600 °C

Vapor residence time: >15 s

Heating rate: 10-300 °C/s

Not assigned
High temperature pyrolysis Temperature: 800-1150 °C

Vapor residence time: 10-100 min

Heating rate: 0.1-1 °C/s

Bio-oil ~43

Biochar~22

Gases~45

History

Oak charcoal

Pyrolysis has been used for turning wood into charcoal since ancient times. The ancient Egyptians used the liquid fraction obtained from the pyrolysis of cedar wood, in their embalming process.

The dry distillation of wood remained the major source of methanol into the early 20th century. Pyrolysis was instrumental in the discovery of many chemical substances, such as phosphorus from ammonium sodium hydrogen phosphate NH4NaHPO4 in concentrated urine, oxygen from mercuric oxide, and various nitrates.

General processes and mechanisms

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:

  • Below about 100 °C, volatiles, including some water, evaporate. Heat-sensitive substances, such as vitamin C and proteins, may partially change or decompose already at this stage.
  • At about 100 °C or slightly higher, any remaining water that is merely absorbed in the material is driven off. This process consumes a lot of energy, so the temperature may stop rising until all water has evaporated. Water trapped in crystal structure of hydrates may come off at somewhat higher temperatures.
  • Some solid substances, like fats, waxes, and sugars, may melt and separate.
  • Between 100 and 500 °C, many common organic molecules break down. Most sugars start decomposing at 160–180 °C. Cellulose, a major component of wood, paper, and cotton fabrics, decomposes at about 350 °C. Lignin, another major wood component, starts decomposing at about 350 °C, but continues releasing volatile products up to 500 °C. The decomposition products usually include water, carbon monoxide CO and/or carbon dioxide CO2, as well as a large number of organic compounds. Gases and volatile products leave the sample, and some of them may condense again as smoke. Generally, this process also absorbs energy. Some volatiles may ignite and burn, creating a visible flame. The non-volatile residues typically become richer in carbon and form large disordered molecules, with colors ranging between brown and black. At this point the matter is said to have been "charred" or "carbonized".
  • At 200–300 °C, if oxygen has not been excluded, the carbonaceous residue may start to burn, in a highly exothermic reaction, often with no or little visible flame. Once carbon combustion starts, the temperature rises spontaneously, turning the residue into a glowing ember and releasing carbon dioxide and/or monoxide. At this stage, some of the nitrogen still remaining in the residue may be oxidized into nitrogen oxides like NO2 and N2O3. Sulfur and other elements like chlorine and arsenic may be oxidized and volatilized at this stage.
  • Once combustion of the carbonaceous residue is complete, a powdery or solid mineral residue (ash) is often left behind, consisting of inorganic oxidized materials of high melting point. Some of the ash may have left during combustion, entrained by the gases as fly ash or particulate emissions. Metals present in the original matter usually remain in the ash as oxides or carbonates, such as potash. Phosphorus, from materials such as bone, phospholipids, and nucleic acids, usually remains as phosphates.

Safety challenges

Because pyrolysis takes place at high temperatures which exceed the autoignition temperature of the produced gases, an explosion risk exists if oxygen is present. To control the temperature of pyrolysis systems careful temperature control is needed and can be accomplished with an open source pyrolysis controller. Pyrolysis also produces various toxic gases, mainly carbon monoxide. The greatest risk of fire, explosion and release of toxic gases comes when the system is starting up and shutting down, operating intermittently, or during operational upsets.

Inert gas purging is essential to manage inherent explosion risks. The procedure is not trivial and failure to keep oxygen out has led to accidents.

Occurrence and uses

Clandestine chemistry

Conversion of CBD to THC can be brought about by pyrolysis.

Cooking

Brownish onions with carrots and celery in a frying pan.
Caramelized onions are slightly pyrolyzed.
 
A blacked bent disc, barely recognizible as a pizza, standing up stiffly from a (fresh, white) plate
This pizza is pyrolyzed, almost completely carbonized.

Pyrolysis has many applications in food preparation. 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 flavor. The distinctive flavors are used in many dishes; for instance, caramelized onion is used in French onion soup. The temperatures needed for caramelization lie above the boiling point of water. Frying oil can easily rise above the 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 time.

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

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. 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 and smoke-burning incinerators as an effective measure to reduce air pollution.

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).

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 the 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. 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. It is a key component of the terra preta soils associated with ancient indigenous communities of the Amazon basin. 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 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.

Liquid and gaseous biofuels

Pyrolysis is the basis of several methods for producing fuel from biomass, i.e. lignocellulosic biomass. 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. 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, and sewage sludge.

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

Synthetic diesel fuel by pyrolysis of organic materials is not yet economically competitive. 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.

The low quality of oils produced through pyrolysis can be improved by physical and chemical processes, 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. Fast pyrolysis is also investigated for biomass conversion. 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 is an industrial process for "turquoise" hydrogen production from methane by removing solid carbon from natural gas. This one-step process produces hydrogen in high volume at low cost (less than steam reforming with carbon sequestration). No greenhouse gas is released. No deep well injection of carbon dioxide is needed. Only water is released when hydrogen is used as the fuel for fuel-cell electric heavy truck transportation, gas turbine electric power generation and hydrogen for industrial processes including producing ammonia fertilizer and cement. Methane pyrolysis is the process operating around 1065 °C for producing hydrogen from natural gas that allows removal of carbon easily (solid carbon is a byproduct of the process). The industrial quality solid carbon can then be sold or landfilled and is not released into the atmosphere, avoiding emission of greenhouse gas (GHG) or ground water pollution from a landfill.

In 2015, a company called Monolith Materials built a pilot plant in Redwood City, CA to study scaling Methane Pyrolysis using renewable power in the process. A successful pilot project then led to a larger commercial-scale demonstration plant in Hallam, Nebraska in 2016. As of 2020, this plant is operational and can produce around 14 metric tons of hydrogen per day.  In 2021, the US Department of Energy backed Monolith Materials' plans for major expansion with a $1B loan guarantee. The funding will help produce a plant capable of generating 164 metric tons of hydrogen per day by 2024. Pilots with gas utilities and biogas plants are underway with companies like Modern Hydrogen. Volume production is also being evaluated in the BASF "methane pyrolysis at scale" pilot plant, the chemical engineering team at University of California - Santa Barbara and in such research laboratories as Karlsruhe Liquid-metal Laboratory (KALLA). Power for process heat consumed is only one-seventh of the power consumed in the water electrolysis method for producing hydrogen.

The Australian company Hazer Group was founded in 2010 to commercialise technology originally developed at the University of Western Australia.  The company was listed on the ASX in December 2015. It is completing a commercial demonstration project to produce renewable hydrogen and graphite from wastewater and iron ore as a process catalyst use technology created by the University of Western Australia (UWA). The Commercial Demonstration Plant project is an Australian first, and expected to produce around 100 tonnes of fuel-grade hydrogen and 380 tonnes of graphite each year starting in 2023. It was scheduled to commence in 2022. "10 December 2021: Hazer Group (ASX: HZR) regret to advise that there has been a delay to the completion of the fabrication of the reactor for the Hazer Commercial Demonstration Project (CDP). This is expected to delay the planned commissioning of the Hazer CDP, with commissioning now expected to occur after our current target date of 1Q 2022." The Hazer Group has collaboration agreements with Engie for a facility in France in May 2023. A Memorandum of Understanding with Chubu Electric & Chiyoda in Japan April 2023 and an agreement with Suncor Energy and FortisBC to develop 2,500 tonnes per Annum Burrard-Hazer Hydrogen Production Plant in Canada April 2022

The American company C-Zero's technology converts natural gas into hydrogen and solid carbon. The hydrogen provides clean, low-cost energy on demand, while the carbon can be permanently sequestered. C-Zero announced in June 2022 that it closed a $34 million financing round led by SK Gas, a subsidiary of South Korea's second-largest conglomerate, the SK Group. SK Gas was joined by two other new investors, Engie New Ventures and Trafigura, one of the world's largest physical commodities trading companies, in addition to participation from existing investors including Breakthrough Energy Ventures, Eni Next, Mitsubishi Heavy Industries, and AP Ventures. Funding was for C-Zero's first pilot plant, which was expected to be online in Q1 2023. The plant may be capable of producing up to 400 kg of hydrogen per day from natural gas with no CO2 emissions.

One of the world's largest chemical companies, BASF, has been researching hydrogen pyrolysis for more than 10 years.

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.

Semiconductors

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. Raw polycrystalline silicon is produced by the chemical vapor deposition of silane gases:

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. 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.

In tire waste management, tire pyrolysis is a well-developed technology. Other products from car tire pyrolysis include steel wires, carbon black and bitumen. The area faces legislative, economic, and marketing obstacles. Oil derived from tire rubber pyrolysis has a high sulfur content, which gives it high potential as a pollutant; consequently it should be desulfurized.

Alkaline pyrolysis of sewage sludge at low temperature of 500 °C can enhance H
2
production with in-situ carbon capture. The use of NaOH (sodium hydroxide) has the potential to produce H
2
-rich gas that can be used for fuels cells directly.

In early November 2021, the U.S. State of Georgia announced a joint effort with Igneo Technologies to build an $85 million large electronics recycling plant in the Port of Savannah. The project will focus on lower-value, plastics-heavy devices in the waste stream using multiple shredders and furnaces using pyrolysis technology.

Waste from pyrolysis itself can also be used for useful products. For example, contaminant-rich retentate from liquid-fed pyrolysis of postconsumer multilayer packaging waste can be used as novel building composite materials, which have higher compression strengths (10-12 MPa) than construction bricks and brickworks (7 MPa), as well as 57% lower density, 0.77 g/cm3 .

One-stepwise pyrolysis and Two-stepwise pyrolysis for Tobacco Waste

Pyrolysis has also been used for trying to mitigate tobacco waste. One method was done where tobacco waste was separated into two categories TLW (Tobacco Leaf Waste) and TSW (Tobacco Stick Waste). TLW was determined to be any waste from cigarettes and TSW was determined to be any waste from electronic cigarettes. Both TLW and TSW were dried at 80 °C for 24 hours and stored in a desiccator. Samples were grounded so that the contents were uniform. Tobacco Waste (TW) also contains inorganic (metal) contents, which was determined using an inductively coupled plasma-optical spectrometer. Thermo-gravimetric analysis was used to thermally degrade four samples (TLW, TSW, glycerol, and guar gum) and monitored under specific dynamic temperature conditions. About one gram of both TLW and TSW were used in the pyrolysis tests. During these analysis tests, CO
2
and N
2
were used as atmospheres inside of a tubular reactor that was built using quartz tubing. For both CO
2
and N
2
atmospheres the flow rate was 100 mL min−1. External heating was created via a tubular furnace. The pyrogenic products were classified into three phases. The first phase was biochar, a solid residue produced by the reactor at 650 °C. The second phase liquid hydrocarbons were collected by a cold solvent trap and sorted by using chromatography. The third and final phase was analyzed using an online micro GC unit and those pyrolysates were gases.

Two different types of experiments were conducted: one-stepwise pyrolysis and two-stepwise pyrolysis. One-stepwise pyrolysis consisted of a constant heating rate (10 °C min−1) from 30 to 720 °C. In the second step of the two-stepwise pyrolysis test the pyrolysates from the one-stepwise pyrolysis were pyrolyzed in the second heating zone which was controlled isothermally at 650 °C. The two-stepwise pyrolysis was used to focus primarily on how well CO
2
affects carbon redistribution when adding heat through the second heating zone.

First noted was the thermolytic behaviors of TLW and TSW in both the CO
2
and N
2
environments. For both TLW and TSW the thermolytic behaviors were identical at less than or equal to 660 °C in the CO
2
and N
2
environments. The differences between the environments start to occur when temperatures increase above 660 °C and the residual mass percentages significantly decrease in the CO
2
environment compared to that in the N
2
environment. This observation is likely due to the Boudouard reaction, where we see spontaneous gasification happening when temperatures exceed 710 °C. Although these observations were seen at temperatures lower than 710 °C it is most likely due to the catalytic capabilities of inorganics in TLW. It was further investigated by doing ICP-OES measurements and found that a fifth of the residual mass percentage was Ca species. CaCO
3
is used in cigarette papers and filter material, leading to the explanation that degradation of CaCO
3
causes pure CO
2
reacting with CaO in a dynamic equilibrium state. This being the reason for seeing mass decay between 660 °C and 710 °C. Differences in differential thermogram (DTG) peaks for TLW were compared to TSW. TLW had four distinctive peaks at 87, 195, 265, and 306 °C whereas TSW had two major drop offs at 200 and 306 °C with one spike in between. The four peaks indicated that TLW contains more diverse types of additives than TSW. The residual mass percentage between TLW and TSW was further compared, where the residual mass in TSW was less than that of TLW for both CO
2
and N
2
environments concluding that TSW has higher quantities of additives than TLW. 

Production of Hydrogen, Methane, and Tars when creating Biochar

The one-stepwise pyrolysis experiment showed different results for the CO
2
and N
2
environments. During this process the evolution of 5 different notable gases were observed. Hydrogen, Methane, Ethane, Carbon Dioxide, and Ethylene all are produced when the thermolytic rate of TLW began to be retarded at greater than or equal to 500 °C. Thermolytic rate begins at the same temperatures for both the CO
2
and N
2
environment but there is higher concentration of the production of Hydrogen, Ethane, Ethylene, and Methane in the N
2
environment than that in the CO
2
environment. The concentration of CO in the CO
2
environment is significantly greater as temperatures increase past 600 °C and this is due to CO
2
being liberated from CaCO
3
in TLW. This significant increase in CO concentration is why there is lower concentrations of other gases produced in the CO
2
environment due to a dilution effect. Since pyrolysis is the re-distribution of carbons in carbon substrates into three pyrogenic products. The CO
2
environment is going to be more effective because the CO
2
reduction into CO allows for the oxidation of pyrolysates to form CO. In conclusion the CO
2
environment allows a higher yield of gases than oil and biochar. When the same process is done for TSW the trends are almost identical therefore the same explanations can be applied to the pyrolysis of TSW.

Harmful chemicals were reduced in the CO
2
environment due to CO formation causing tar to be reduced. One-stepwise pyrolysis was not that effective on activating CO
2
on carbon rearrangement due to the high quantities of liquid pyrolysates (tar). Two-stepwise pyrolysis for the CO
2
environment allowed for greater concentrations of gases due to the second heating zone. The second heating zone was at a consistent temperature of 650 °C isothermally. More reactions between CO
2
and gaseous pyrolysates with longer residence time meant that CO
2
could further convert pyrolysates into CO. The results showed that the two-stepwise pyrolysis was an effective way to decrease tar content and increase gas concentration by about 10 wt.% for both TLW (64.20 wt.%) and TSW (73.71%).

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 and static mixers. During the thermal cleaning process, at temperatures from 310 to 540 °C (600 to 1,000 °F), organic material is converted by pyrolysis and oxidation into volatile organic compounds, hydrocarbons and carbonized gas. Inorganic elements remain.

Several types of thermal cleaning systems use pyrolysis:

  • Molten Salt Baths belong to the oldest thermal cleaning systems; cleaning with a molten 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 toxic hydrogen cyanide gas.
  • Fluidized Bed Systems use sand or aluminium oxide as heating medium; these systems also clean very fast but the medium does not melt or boil, nor emit any vapors or odors; the cleaning process takes one to two hours.
  • Vacuum Ovens use pyrolysis in a vacuum avoiding uncontrolled combustion inside the cleaning chamber; the cleaning process takes 8 to 30 hours.
  • Burn-Off Ovens, also known as Heat-Cleaning Ovens, are gas-fired and used in the painting, coatings, electric 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 (B
2
H
6
) at ca. 200 °C. Products include the clusters pentaborane and decaborane. These pyrolyses involve not only cracking (to give H
2
), but also recondensation.

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

Other uses and occurrences

  • Pyrolysis is used to turn organic materials into carbon for the purpose of carbon-14 dating.
  • Pyrolysis liquids from slow pyrolysis of bark and hemp have been tested for their antifungal activity against wood decaying fungi, showing potential to substitute the current wood preservatives while further tests are still required. However, their ecotoxicity is very variable and while some are less toxic than current wood preservatives, other pyrolysis liquids have shown high ecotoxicity, what may cause detrimental effects in the environment.
  • Pyrolysis of tobacco, paper, and additives, in cigarettes and other products, generates many volatile products (including nicotine, carbon monoxide, and tar) that are responsible for the aroma and negative health effects of smoking. Similar considerations apply to the smoking of marijuana and the burning of incense products and mosquito coils.
  • Pyrolysis occurs during the incineration of trash, potentially generating volatiles that are toxic or contribute to air pollution if not completely burned.
  • Laboratory or industrial equipment sometimes gets fouled by carbonaceous residues that result from coking, the pyrolysis of organic products that come into contact with hot surfaces.

PAHs generation

Polycyclic aromatic hydrocarbons (PAHs) can be generated from the pyrolysis of different solid waste fractions, 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.

When the temperature is increased from 500 to 900 °C, most PAHs increase. With increasing temperature, the percentage of light PAHs decreases and the percentage of heavy PAHs increases.

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. Activation energies can be calculated using the Kissinger method or peak analysis-least square method (PA-LSM).

TGA can couple with Fourier-transform infrared spectroscopy (FTIR) and mass spectrometry. As the temperature increases, the volatiles generated from pyrolysis can be measured.

Macro-TGA

In TGA, the 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-scale samples to investigate the effects of pyrolysis with mass and heat transfer.

Pyrolysis–gas chromatography–mass spectrometry

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

Machine learning

In recent years, machine learning has attracted significant research interest in predicting yields, optimizing parameters, and monitoring pyrolytic processes.

Broca's area

From Wikipedia, the free encyclopedia
 
Broca's area
Broca's area is made up of Brodmann areas 44 (pars opercularis) and 45 (pars triangularis).
 
Broca's area (shown in red)

Broca's area, or the Broca area (/ˈbrkə/, also UK: /ˈbrɒkə/, US: /ˈbrkɑː/), is a region in the frontal lobe of the dominant hemisphere, usually the left, of the brain with functions linked to speech production.

Language processing has been linked to Broca's area since Pierre Paul Broca reported impairments in two patients. They had lost the ability to speak after injury to the posterior inferior frontal gyrus (pars triangularis) (BA45) of the brain. Since then, the approximate region he identified has become known as Broca's area, and the deficit in language production as Broca's aphasia, also called expressive aphasia. Broca's area is now typically defined in terms of the pars opercularis and pars triangularis of the inferior frontal gyrus, represented in Brodmann's cytoarchitectonic map as Brodmann area 44 and Brodmann area 45 of the dominant hemisphere.

Functional magnetic resonance imaging (fMRI) has shown language processing to also involve the third part of the inferior frontal gyrus the pars orbitalis, as well as the ventral part of BA6 and these are now often included in a larger area called Broca's region.

Studies of chronic aphasia have implicated an essential role of Broca's area in various speech and language functions. Further, fMRI studies have also identified activation patterns in Broca's area associated with various language tasks. However, slow destruction of Broca's area by brain tumors can leave speech relatively intact, suggesting its functions can shift to nearby areas in the brain.

Structure

Brodmann area 44
Brodmann area 45

Broca's area is often identified by visual inspection of the topography of the brain either by macrostructural landmarks such as sulci or by the specification of coordinates in a particular reference space. The currently used Talairach and Tournoux atlas projects Brodmann's cytoarchitectonic map onto a template brain. Because Brodmann's parcelation was based on subjective visual inspection of cytoarchitectonic borders and also Brodmann analyzed only one hemisphere of one brain, the result is imprecise. Further, because of considerable variability across brains in terms of shape, size, and position relative to sulcal and gyral structure, a resulting localization precision is limited.

Nevertheless, Broca's area in the left hemisphere and its homologue in the right hemisphere are designations usually used to refer to the triangular part of inferior frontal gyrus (PTr) and the opercular part of inferior frontal gyrus (POp). The PTr and POp are defined by structural landmarks that only probabilistically divide the inferior frontal gyrus into anterior and posterior cytoarchitectonic areas of 45 and 44, respectively, by Brodmann's classification scheme.

Area 45 receives more afferent connections from the prefrontal cortex, the superior temporal gyrus, and the superior temporal sulcus, compared to area 44, which tends to receive more afferent connections from motor, somatosensory, and inferior parietal regions.

The differences between area 45 and 44 in cytoarchitecture and in connectivity suggest that these areas might perform different functions. Indeed, recent neuroimaging studies have shown that the PTr and Pop, corresponding to areas 45 and 44, respectively, play different functional roles in the human with respect to language comprehension and action recognition/understanding.

The Broca's area is about 20% larger in women than in men.

Functions

Language comprehension

For a long time, it was assumed that the role of Broca's area was more devoted to language production than language comprehension. However, there is evidence to demonstrate that Broca's area also plays a significant role in language comprehension. Patients with lesions in Broca's area who exhibit agrammatical speech production also show inability to use syntactic information to determine the meaning of sentences. Also, a number of neuroimaging studies have implicated an involvement of Broca's area, particularly of the pars opercularis of the left inferior frontal gyrus, during the processing of complex sentences. Further, functional magnetic resonance imaging (fMRI) experiments have shown that highly ambiguous sentences result in a more activated inferior frontal gyrus. Therefore, the activity level in the inferior frontal gyrus and the level of lexical ambiguity are directly proportional to each other, because of the increased retrieval demands associated with highly ambiguous content.

There is also specialisation for particular aspects of comprehension within Broca's area. Work by Devlin et al. (2003) showed in a repetitive transcranial magnetic stimulation (rTMS) study that there was an increase in reaction times when performing a semantic task under rTMS aimed at the pars triangularis (situated in the anterior part of Broca's area). The increase in reaction times is indicative that that particular area is responsible for processing that cognitive function. Disrupting these areas via TMS disrupts computations performed in the areas leading to an increase in time needed to perform the computations (reflected in reaction times). Later work by Nixon et al. (2004) showed that when the pars opercularis (situated in the posterior part of Broca's area) was stimulated under rTMS there was an increase in reaction times in a phonological task. Gough et al. (2005) performed an experiment combining elements of these previous works in which both phonological and semantic tasks were performed with rTMS stimulation directed at either the anterior or the posterior part of Broca's area. The results from this experiment conclusively distinguished anatomical specialisation within Broca's area for different components of language comprehension. Here the results showed that under rTMS stimulation:

  • Semantic tasks only showed a decrease in reaction times when stimulation was aimed at the anterior part of Broca's area (where a decrease of 10% (50 ms) was seen compared to a no-TMS control group)
  • Phonological tasks showed a decrease in reaction times when stimulation was aimed at the posterior part of Broca's area (where a decrease of 6% (30 ms) was seen compared to control)

To summarise, the work above shows anatomical specialisation in Broca's area for language comprehension, with the anterior part of Broca's area responsible for understanding the meaning of words (semantics) and the posterior part of Broca's area responsible for understanding how words sound (phonology).

Action recognition and production

Experiments have indicated that Broca's area is involved in various cognitive and perceptual tasks. One important contribution of Brodmann's area 44 is also found in the motor-related processes. Observation of meaningful hand shadows resembling moving animals activates frontal language area, demonstrating that Broca's area indeed plays a role in interpreting action of others. An activation of BA 44 was also reported during execution of grasping and manipulation.

Speech-associated gestures

It has been speculated that because speech-associated gestures could possibly reduce lexical or sentential ambiguity, comprehension should improve in the presence of speech-associated gestures. As a result of improved comprehension, the involvement of Broca's area should be reduced.

Many neuroimaging studies have also shown activation of Broca's area when representing meaningful arm gestures. A recent study has shown evidence that word and gesture are related at the level of translation of particular gesture aspects such as its motor goal and intention. This finding helps explain why, when this area is defective, those who use sign language also have language deficits. This finding, that aspects of gestures are translated in words within Broca's area, also explains language development in terms of evolution. Indeed, many authors have proposed that speech evolved from a primitive communication that arose from gestures.

Speaking without Broca's area

Damage to Broca's area is commonly associated with telegraphic speech made up of content vocabulary. For example, a person with Broca's aphasia may say something like, "Drive, store. Mom." meaning to say, "My mom drove me to the store today." Therefore, the content of the information is correct, but the grammar and fluidity of the sentence is missing.

The essential role of the Broca's area in speech production has been questioned since it can be destroyed while leaving language nearly intact. In one case of a computer engineer, a slow-growing glioma tumor was removed. The tumor and the surgery destroyed the left inferior and middle frontal gyrus, the head of the caudate nucleus, the anterior limb of the internal capsule, and the anterior insula. However, there were minimal language problems three months after removal and the individual returned to his professional work. These minor problems include the inability to create syntactically complex sentences including more than two subjects, multiple causal conjunctions, or reported speech. These were explained by researchers as due to working memory problems. They also attributed his lack of problems to extensive compensatory mechanisms enabled by neural plasticity in the nearby cerebral cortex and a shift of some functions to the homologous area in the right hemisphere.

Clinical significance

Stuttering

A speech disorder known as stuttering is seen to be associated with underactivity in Broca's area.

Aphasia

Aphasia is an acquired language disorder affecting all modalities such as writing, reading, speaking, and listening and results from brain damage. It is often a chronic condition that creates changes in all areas of one's life.

Expressive aphasia vs. other aphasias

Patients with expressive aphasia, also known as Broca's aphasia, are individuals who know "what they want to say, they just cannot get it out". They are typically able to comprehend words, and sentences with a simple syntactic structure (see above), but are more or less unable to generate fluent speech. Other symptoms that may be present include problems with fluency, articulation, word-finding, word repetition, and producing and comprehending complex grammatical sentences, both orally and in writing.

This specific group of symptoms distinguishes those who have expressive aphasia from individuals with other types of aphasia. There are several distinct "types" of aphasia, and each type is characterized by a different set of language deficits. Although those who have expressive aphasia tend to retain good spoken language comprehension, other types of aphasia can render patients completely unable to understand any language at all, unable to understand any spoken language (auditory verbal agnosia), whereas still other types preserve language comprehension, but with deficits. People with expressive aphasia may struggle less with reading and writing (see alexia) than those with other types of aphasia. Although individuals with expressive aphasia tend to have a good ability to self-monitor their language output (they "hear what they say" and make corrections), other types of aphasics can seem entirely unaware of their language deficits.

In the classical sense, expressive aphasia is the result of injury to Broca's area; it is often the case that lesions in specific brain areas cause specific, dissociable symptoms, although case studies show there is not always a one-to-one mapping between lesion location and aphasic symptoms. The correlation between damage to certain specific brain areas (usually in the left hemisphere) and the development of specific types of aphasia makes it possible to deduce (albeit very roughly) the location of a suspected brain lesion based only on the presence (and severity) of a certain type of aphasia, though this is complicated by the possibility that a patient may have damage to a number of brain areas and may exhibit symptoms of more than one type of aphasia. The examination of lesion data in order to deduce which brain areas are essential in the normal functioning of certain aspects of cognition is called the deficit-lesion method; this method is especially important in the branch of neuroscience known as aphasiology. Cognitive science – to be specific, cognitive neuropsychology – are branches of neuroscience that also make extensive use of the deficit-lesion method.

Major characteristics of different types of acute aphasia
Type of aphasia Speech repetition Naming Auditory comprehension Fluency
Expressive aphasia Moderate–severe Moderate–severe Mild difficulty Non-fluent, effortful, slow
Receptive aphasia Mild–severe Mild–severe Defective Fluent paraphasic
Conduction aphasia Poor Poor Relatively good Fluent
Mixed transcortical aphasia Moderate Poor Poor Non-fluent
Transcortical motor aphasia Good Mild–severe Mild Non-fluent
Transcortical sensory aphasia Good Moderate–severe Poor Fluent
Global aphasia Poor Poor Poor Non-fluent
Anomic aphasia Mild Moderate–severe Mild Fluent

Since studies carried out in the late 1970s it has been understood that the relationship between Broca's area and Broca's aphasia is not as consistent as once thought. Lesions to Broca's area alone do not result in Broca's aphasia, nor do Broca's aphasic patients necessarily have lesions in Broca's area. Lesions to Broca's area alone are known to produce a transient mutism that resolves within 3–6 weeks. This discovery suggests that Broca's area may be included in some aspect of verbalization or articulation; however, this does not address its part in sentence comprehension. Still, Broca's area frequently emerges in functional imaging studies of sentence processing. However, it also becomes activated in word-level tasks. This suggests that Broca's area is not dedicated to sentence processing alone, but supports a function common to both. In fact, Broca's area can show activation in such non-linguistic tasks as imagery of motion.

Considering the hypothesis that Broca's area may be most involved in articulation, its activation in all of these tasks may be due to subjects' covert articulation while formulating a response. Despite this caveat, a consensus seems to be forming that whatever role Broca's area may play, it may relate to known working memory functions of the frontal areas. (There is a wide distribution of Talairach coordinates reported in the functional imaging literature that are referred to as part of Broca's area.) The processing of a passive voice sentence, for example, may require working memory to assist in the temporary retention of information while other relevant parts of the sentence are being manipulated (i.e. to resolve the assignment of thematic roles to arguments). Miyake, Carpenter, and Just have proposed that sentence processing relies on such general verbal working memory mechanisms, while Caplan and Waters consider Broca's area to be involved in working memory specifically for syntactic processing. Friederici (2002) breaks Broca's area into its component regions and suggests that Brodmann's area 44 is involved in working memory for both phonological and syntactic structure. This area becomes active first for phonology and later for syntax as the time course for the comprehension process unfolds. Brodmann's area 45 and Brodmann's area 47 are viewed as being specifically involved in working memory for semantic features and thematic structure where processes of syntactic reanalysis and repair are required. These areas come online after Brodmann's area 44 has finished its processing role and are active when comprehension of complex sentences must rely on general memory resources. All of these theories indicate a move towards a view that syntactic comprehension problems arise from a computational rather than a conceptual deficit. Newer theories take a more dynamic view of how the brain integrates different linguistic and cognitive components and are examining the time course of these operations.

Neurocognitive studies have already implicated frontal areas adjacent to Broca's area as important for working memory in non-linguistic as well as linguistic tasks. Cabeza and Nyberg's analysis of imaging studies of working memory supports the view that BA45/47 is recruited for selecting or comparing information, while BA9/46 might be more involved in the manipulation of information in working memory. Since large lesions are typically required to produce a Broca's aphasia, it is likely that these regions may also become compromised in some patients and may contribute to their comprehension deficits for complex morphosyntactic structures.

Broca's area as a key center in the linking of phonemic sequences

Broca's area has been previously associated with a variety of processes, including phonological segmentation, syntactic processing, and unification, all of which involve segmenting and linking different types of linguistic information. Although repeating and reading single words does not engage semantic and syntactic processing, it does require an operation linking phonemic sequences with motor gestures. Findings indicate that this linkage is coordinated by Broca's area through reciprocal interactions with temporal and frontal cortices responsible for phonemic and articulatory representations, respectively, including interactions with the motor cortex before the actual act of speech. Based on these unique findings, it has been proposed that Broca's area is not the seat of articulation, but rather is a key node in manipulating and forwarding neural information across large-scale cortical networks responsible for key components of speech production.

History

In a study published in 2007, the preserved brains of both Leborgne and Lelong (patients of Broca) were reinspected using high-resolution volumetric MRI. The purpose of this study was to scan the brains in three dimensions and to identify the extent of both cortical and subcortical lesions in more detail. The study also sought to locate the exact site of the lesion in the frontal lobe in relation to what is now called Broca's area with the extent of subcortical involvement.

Broca's patients

Louis Victor Leborgne (Tan)

Leborgne was a patient of Broca's. At 30 years old, he was almost completely unable to produce any words or phrases. He was able to repetitively produce only the word temps (French word for "time"). After his death, a neurosyphilitic lesion was discovered on the surface of his left frontal lobe.

Lelong

Lelong was another patient of Broca's. He also exhibited reduced productive speech. He could only say five words, 'yes', 'no', 'three', 'always', and 'lelo' (a mispronunciation of his own name). A lesion within the lateral frontal lobe was discovered during Lelong's autopsy. Broca's previous patient, Leborgne, had a lesion in the same area of his frontal lobe. These two cases led Broca to believe that speech was localized to this particular area.

MRI findings

Examination of the brains of Broca's two historic patients with high-resolution MRI has produced several interesting findings. First, the MRI findings suggest that other areas besides Broca's area may also have contributed to the patients' reduced productive speech. This finding is significant because it has been found that, though lesions to Broca's area alone can possibly cause temporary speech disruption, they do not result in severe speech arrest. Therefore, there is a possibility that the aphasia denoted by Broca as an absence of productive speech also could have been influenced by the lesions in the other region. Another finding is that the region, which was once considered to be critical for speech by Broca, is not precisely the same region as what is now known as Broca's area. This study provides further evidence to support the claim that language and cognition are far more complicated than once thought and involve various networks of brain regions.

Evolution of language

The pursuit of a satisfying theory that addresses the origin of language in humans has led to the consideration of a number of evolutionary "models". These models attempt to show how modern language might have evolved, and a common feature of many of these theories is the idea that vocal communication was initially used to complement a far more dominant mode of communication through gesture. Human language might have evolved as the "evolutionary refinement of an implicit communication system already present in lower primates, based on a set of hand/mouth goal-directed action representations."

"Hand/mouth goal-directed action representations" is another way of saying "gestural communication", "gestural language", or "communication through body language". The recent finding that Broca's area is active when people are observing others engaged in meaningful action is evidence in support of this idea. It was hypothesized that a precursor to the modern Broca's area was involved in translating gestures into abstract ideas by interpreting the movements of others as meaningful action with an intelligent purpose. It is argued that over time the ability to predict the intended outcome and purpose of a set of movements eventually gave this area the capability to deal with truly abstract ideas, and therefore (eventually) became capable of associating sounds (words) with abstract meanings. The observation that frontal language areas are activated when people observe hand shadows is further evidence that human language may have evolved from existing neural substrates that evolved for the purpose of gesture recognition. The study, therefore, claims that Broca's area is the "motor center for speech", which assembles and decodes speech sounds in the same way it interprets body language and gestures. Consistent with this idea is that the neural substrate that regulated motor control in the common ancestor of apes and humans was most likely modified to enhance cognitive and linguistic ability. Studies of speakers of American Sign Language and English suggest that the human brain recruited systems that had evolved to perform more basic functions much earlier; these various brain circuits, according to the authors, were tapped to work together in creating language.

Another recent finding has showed significant areas of activation in subcortical and neocortical areas during the production of communicative manual gestures and vocal signals in chimpanzees. Further, the data indicating that chimpanzees intentionally produce manual gestures as well as vocal signals to communicate with humans suggests that the precursors to human language are present at both the behavioral and neuronanatomical levels. More recently, the neocortical distribution of activity-dependent gene expression in marmosets provided direct evidence that the ventrolateral prefrontal cortex, which comprises Broca's area in humans and has been associated with auditory processing of species-specific vocalizations and orofacial control in macaques, is engaged during vocal output in a New World monkey. These findings putatively set the origin of vocalization-related neocortical circuits to at least 35 million years ago, when the Old and New World monkey lineages split.

Conflagration

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