Pyrolysis

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Not to be confused with Pyrrolysine.
Simplified depiction of pyrolysis chemistry.

Pyrolysis is a thermochemical decomposition of organic material at elevated temperatures in the absence of oxygen (or any halogen). It involves the simultaneous change of chemical composition and physical phase, and is irreversible. The word is coined from the Greek-derived elements pyro "fire" and lysis "separating".

Pyrolysis is a type of thermolysis, and is most commonly observed in organic materials exposed to high temperatures. It is one of the processes involved in charring wood, starting at 200–300 °C (390–570 °F).[1] It also occurs in fires where solid fuels are burning or when vegetation comes into contact with lava in volcanic eruptions. In general, pyrolysis of organic substances produces gas and liquid products and leaves a solid residue richer in carbon content, char. Extreme pyrolysis, which leaves mostly carbon as the residue, is called carbonization.

The process is used heavily in the chemical industry, for example, to produce charcoal, activated carbon, methanol, and other chemicals from wood, to convert ethylene dichloride into vinyl chloride to make PVC, to produce coke from coal, to convert biomass into syngas and biochar, to turn waste into safely disposable substances, and for transforming medium-weight hydrocarbons from oil into lighter ones like gasoline. These specialized uses of pyrolysis may be called various names, such as dry distillation, destructive distillation, or cracking. Pyrolysis is also used in the creation of nanoparticles,[2] zirconia[3] and oxides[4] utilizing an ultrasonic nozzle in a process called ultrasonic spray pyrolysis (USP).

Pyrolysis also plays an important role in several cooking procedures, such as baking, frying, grilling, and caramelizing. In addition, it is a tool of chemical analysis, for example, in mass spectrometry and in carbon-14 dating. Indeed, many important chemical substances, such as phosphorus and sulfuric acid, were first obtained by this process. Pyrolysis has been assumed to take place during catagenesis, the conversion of buried organic matter to fossil fuels. It is also the basis of pyrography. In their embalming process, the ancient Egyptians used a mixture of substances, including methanol, which they obtained from the pyrolysis of wood.

Pyrolysis differs from other high-temperature processes like combustion and hydrolysis in that it usually does not involve reactions with oxygen, water, or any other reagents. In practice, it is not possible to achieve a completely oxygen-free atmosphere. Because some oxygen is present in any pyrolysis system, a small amount of oxidation occurs.

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.

Occurrence and uses[edit]

Fire[edit]

Pyrolysis is usually the first chemical reaction that occurs in the burning of many solid organic fuels, like wood, cloth, and paper, and also of some kinds of plastic. In a wood fire, the visible flames are not due to combustion of the wood itself, but rather of the gases released by its pyrolysis, whereas the flame-less burning of a solid, called smouldering, is the combustion of the solid residue (char or charcoal) left behind by pyrolysis. Thus, the pyrolysis of common materials like wood, plastic, and clothing is extremely important for fire safety and firefighting.

Cooking[edit]

Pyrolysis occurs whenever food is exposed to high enough temperatures in a dry environment, such as roasting, baking, toasting, or grilling. It is the chemical process responsible for the formation of the golden-brown crust in foods prepared by those methods.

In normal cooking, the main food components that undergo pyrolysis are carbohydrates (including sugars, starch, and fibre) and proteins. (See: Maillard reaction.) Pyrolysis of fats requires a much higher temperature, and, since it produces toxic and flammable products (such as acrolein), it is, in general, avoided in normal cooking. It may occur, however, when grilling fatty meats over hot coals.

Even though cooking is normally carried out in air, the temperatures and environmental conditions are such that there is little or no combustion of the original substances or their decomposition products. In particular, the pyrolysis of proteins and carbohydrates begins at temperatures much lower than the ignition temperature of the solid residue, and the volatile subproducts are too diluted in air to ignite. (In flambé dishes, the flame is due mostly to combustion of the alcohol, while the crust is formed by pyrolysis as in baking.)

Pyrolysis of carbohydrates and proteins requires temperatures substantially higher than 100 °C (212 °F), so pyrolysis does not occur as long as free water is present, e.g., in boiling food — not even in a pressure cooker. When heated in the presence of water, carbohydrates and proteins suffer gradual hydrolysis rather than pyrolysis. Indeed, for most foods, pyrolysis is usually confined to the outer layers of food, and begins only after those layers have dried out.

Food pyrolysis temperatures are, however, lower than the boiling point of lipids, so pyrolysis occurs when frying in vegetable oil or suet, or basting meat in its own fat.

Pyrolysis also plays an essential role in the production of barley tea, coffee, and roasted nuts such as peanuts and almonds. As these consist mostly of dry materials, the process of pyrolysis is not limited to the outermost layers but extends throughout the materials. In all these cases, pyrolysis creates or releases many of the substances that contribute to the flavor, color, and biological properties of the final product. It may also destroy some substances that are toxic, unpleasant in taste, or those that may contribute to spoilage.

Controlled pyrolysis of sugars starting at 170 °C (338 °F) produces caramel, a beige to brown water-soluble product widely used in confectionery and (in the form of caramel coloring) as a coloring agent for soft drinks and other industrialized food products.

Solid residue from the pyrolysis of spilled and splattered food creates the brown-black encrustation often seen on cooking vessels, stove tops, and the interior surfaces of ovens.

Charcoal[edit]

Pyrolysis has been used since ancient times for turning wood into charcoal on an industrial scale. Besides wood, the process can also use sawdust and other wood waste products.

Charcoal is obtained by heating wood until its complete pyrolysis (carbonization) occurs, leaving only carbon and inorganic ash. In many parts of the world, charcoal is still produced semi-industrially, by burning a pile of wood that has been mostly covered with mud or bricks. The heat generated by burning part of the wood and the volatile byproducts pyrolyzes the rest of the pile. The limited supply of oxygen prevents the charcoal from burning. A more modern alternative is to heat the wood in an airtight metal vessel, which is much less polluting and allows the volatile products to be condensed.

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[edit]

Residues of incomplete organic pyrolysis, e.g., from cooking fires, are thought to be the key component of the terra preta soils associated with ancient indigenous communities of the Amazon basin.[5] 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.

Biochar improves the soil texture and ecology, increasing its ability to retain fertilizers and release them slowly. It naturally contains many of the micronutrients needed by plants, such as selenium. It is also safer than other "natural" fertilizers such as animal manure, since it has been disinfected at high temperature. And, since it releases its nutrients at a slow rate, it greatly reduces the risk of water table contamination.[6]

Biochar is also being considered for carbon sequestration, with the aim of mitigation of global warming.[7][8][9] The solid, carbon-containing char produced can be sequestered in the ground, where it will remain for several hundred to a few thousand years.[10]

Coke[edit]

Pyrolysis is used on a massive scale to turn coal into coke for metallurgy, especially steelmaking. Coke can also be produced from the solid residue left from petroleum refining.

Those starting materials typically contain hydrogen, nitrogen, or oxygen atoms combined with carbon into molecules of medium to high molecular weight. The coke-making or "coking" process consists of heating the material in closed vessels to very high temperatures (up to 2,000 °C or 3,600 °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.

Carbon fiber[edit]

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.

Pyrolytic carbon[edit]

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.[11]

Biofuel[edit]

Pyrolysis is the basis of several methods that are being developed for producing fuel from biomass, which may include either crops grown for the purpose or biological waste products from other industries.[12] 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. Crops and plant material wastes provide biomass feedstock on the basis of their lignocellulose portions.

Although synthetic diesel fuel cannot yet be produced directly by pyrolysis of organic materials, there is a way to produce similar liquid (bio-oil) that can be used as a fuel, after the removal of valuable bio-chemicals that can be used as food additives or pharmaceuticals.[13] Higher efficiency is achieved by the so-called 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.

Fuel bio-oil can also be produced by hydrous pyrolysis from many kinds of feedstock, including waste from pig and turkey farming, by a process called thermal depolymerization (which may, however, include other reactions besides pyrolysis).

Plastic waste disposal[edit]

Anhydrous pyrolysis can also be used to produce liquid fuel similar to diesel from plastic waste, with a higher cetane value and lower sulphur content than traditional diesel.[14] Using pyrolysis to extract fuel from end-of-life plastic is a second-best option after recycling, is environmentally preferable to landfill, and can help reduce dependency on foreign fossil fuels and geo-extraction.[15] Pilot Jeremy Roswell plans to make the first flight from Sydney to London using diesel fuel from recycled plastic waste manufactured by Cynar PLC.[13][16][17]

Waste tire disposal[edit]

Pyrolysis of scrap or waste tires (WT) can separate solids in the tire, such as steel and carbon black, from volatile liquid and gaseous compounds that can be used as fuel. Although the pyrolysis of WT has been widely developed throughout the world, there are legislative, economic, and marketing obstacles to widespread adoption.[18]

Processes[edit]

In many industrial applications, the process is done under pressure and at operating temperatures above 430 °C (806 °F). For agricultural waste, for example, typical temperatures are 450 to 550 °C (840 to 1,000 °F).

Processes[edit]

Since pyrolysis is endothermic,[19] various methods to provide heat to the reacting biomass particles have been proposed:

  • Partial combustion of the biomass products through air injection. This results in poor-quality products.
  • Direct heat transfer with a hot gas, the ideal one being product gas that is reheated and recycled. The problem is to provide enough heat with reasonable gas flow-rates.
  • Indirect heat transfer with exchange surfaces (wall, tubes). It is difficult to achieve good heat transfer on both sides of the heat exchange surface.
  • Direct heat transfer with circulating solids: Solids transfer heat between a burner and a pyrolysis reactor. This is an effective but complex technology.

For flash pyrolysis, the biomass must be ground into fine particles and the insulating char layer that forms at the surface of the reacting particles must be continuously removed. The following technologies have been proposed for biomass pyrolysis:[20]

  • Fixed beds used for the traditional production of charcoal. Poor, slow heat transfer result in very low liquid yields.
  • Augers: This technology is adapted from a Lurgi process for coal gasification. Hot sand and biomass particles are fed at one end of a screw. The screw mixes the sand and biomass and conveys them along. It provides a good control of the biomass residence time. It does not dilute the pyrolysis products with a carrier or fluidizing gas. However, sand must be reheated in a separate vessel, and mechanical reliability is a concern. There is no large-scale commercial implementation.
  • Ablative processes: Biomass particles are moved at high speed against a hot metal surface. Ablation of any char forming at a particle's surface maintains a high rate of heat transfer. This can be achieved by using a metal surface spinning at high speed within a bed of biomass particles, which may present mechanical reliability problems but prevents any dilution of the products. As an alternative, the particles may be suspended in a carrier gas and introduced at high speed through a cyclone whose wall is heated; the products are diluted with the carrier gas.[21] A problem shared with all ablative processes is that scale-up is made difficult, since the ratio of the wall surface to the reactor volume decreases as the reactor size is increased.[22] There is no large-scale commercial implementation.
  • Rotating cone: Pre-heated hot sand and biomass particles are introduced into a rotating cone. Due to the rotation of the cone, the mixture of sand and biomass is transported across the cone surface by centrifugal force. The process is offered by BTG-BTL, a subsidiary from BTG Biomass Technology Group B.V. in The Netherlands. Like other shallow transported-bed reactors relatively fine particles (several mm) are required to obtain a liquid yield of around 70 wt.%. Larger-scale commercial implementation (up to 5 t/h input) is underway.[23]
  • Fluidized beds: Biomass particles are introduced into a bed of hot sand fluidized by a gas, which is usually a recirculated product gas. High heat transfer rates from fluidized sand result in rapid heating of biomass particles. There is some ablation by attrition with the sand particles, but it is not as effective as in the ablative processes. Heat is usually provided by heat exchanger tubes through which hot combustion gas flows. There is some dilution of the products, which makes it more difficult to condense and then remove the bio-oil mist from the gas exiting the condensers. This process has been scaled up by companies such as Dynamotive and Agri-Therm. The main challenges are in improving the quality and consistency of the bio-oil.
  • Circulating fluidized beds: Biomass particles are introduced into a circulating fluidized bed of hot sand. Gas, sand, and biomass particles move together, with the transport gas usually being a recirculated product gas, although it may also be a combustion gas. High heat transfer rates from sand ensure rapid heating of biomass particles and ablation stronger than with regular fluidized beds. A fast separator separates the product gases and vapors from the sand and char particles. The sand particles are reheated in a fluidized burner vessel and recycled to the reactor. Although this process can be easily scaled up, it is rather complex and the products are much diluted, which greatly complicates the recovery of the liquid products.
  • Chain Grate: Dry biomass is fed onto a hot (500C) heavy cast metal grate or apron which forms a continuous loop. A small amount of air aids in heat transfer and in primary reactions for drying and carbonization. Volatile products are combusted for process and boiler heating.

Use of vacuum[edit]

In vacuum pyrolysis, organic material is heated in a vacuum in order to decrease its boiling point and avoid adverse chemical reactions. It is used in organic chemistry as a synthetic tool. In flash vacuum thermolysis or FVT, the residence time of the substrate at the working temperature is limited as much as possible, again in order to minimize secondary reactions. Thus, a synthesis of 2-Furonitrile has been described employing the dehydration of 2-furoic acid amide or oxime via flash vacuum pyrolysis over molecular sieves in the gas phase.[24]

Industrial sources[edit]

Many sources of organic matter can be used as feedstock for pyrolysis. Suitable plant material includes greenwaste, sawdust, waste wood, woody weeds; and agricultural sources including nut shells, straw, cotton trash, rice hulls, switch grass; and animal waste including poultry litter, dairy manure, and potentially other manures. Pyrolysis is used as a form of thermal treatment to reduce waste volumes of domestic refuse. Some industrial byproducts are also suitable feedstock including paper sludge and distillers grain.[25]

There is also the possibility of integrating with other processes such as mechanical biological treatment and anaerobic digestion.[26]

Industrial products[edit]

  • syngas (flammable mixture of carbon monoxide and hydrogen): can be produced in sufficient quantities to provide both the energy needed for pyrolysis and some excess production[7][27]
  • solid char that can either be burned for energy or be recycled as a fertilizer (biochar).

Fire protection[edit]

Destructive fires in buildings will often burn with limited oxygen supply, resulting in pyrolysis reactions. Thus, pyrolysis reaction mechanisms and the pyrolysis properties of materials are important in fire protection engineering for passive fire protection. Pyrolytic carbon is also important to fire investigators as a tool for discovering origin and cause of fires.

Chemistry[edit]

Current research examines the multiple reaction pathways of pyrolysis to understand how to manipulate the formation of pyrolysis' multiple products (oil, gas, char, and miscellaneous chemicals) to enhance the economic value of pyrolysis; identifying catalysts to manipulate pyrolysis reactions is also a goal of some pyrolysis research. Published research suggests that pyrolysis reactions have some dependence upon the structural composition of feedstocks (e.g. lignocellulosic biomass), with contributions from some minerals present in the feedstocks; some minerals present in feedstock are thought to increase the cost of operation of pyrolysis or decrease the value of oil produced from pyrolysis, through corrosive reactions.[28]

See also[edit]

References[edit]

  1. ^ Burning of wood, InnoFireWood's website. Accessed on 2010-02-06.
  2. ^ Kalyana C. Pingali, David A. Rockstraw, and Shuguang Deng, 2005, "Silver Nanoparticles from Ultrasonic Spray Pyrolysis of Aqueous Silver Nitrate," Aerosol Science and Technology, 39:1010-1014
  3. ^ Y. L. Song, S. C. Tsai, C. Y. Chen, T. K. Tseng, C. S. Tsai, J. W. Chen, and Y. D. Yao, 2004, "Ultrasonic Spray Pyrolysis for Synthesis of Spherical Zirconia Particles" Journal of the American Ceramic Society, Vol.87, No. 10
  4. ^ Hoda Amani Hamedani, 2008, Investigation of Deposition Parameters in Ultrasonic Spray Pyrolysis for Fabrication of Solid Oxide Fuel Cell Cathode, Georgia Institute of Technology
  5. ^ Lehmann, Johannes. "Biochar: the new frontier". Archived from the original on 2008-06-18. Retrieved 2008-07-10. 
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  7. ^ a b Horstman, Mark (2007-09-23). "Agrichar – A solution to global warming?". ABC TV Science: Catalyst (Australian Broadcasting Corporation). Retrieved 2008-07-10. 
  8. ^ "Trial to reverse global warming". BBC News. 2009-04-09. Retrieved 2009-04-21. 
  9. ^ "The virtues of biochar: A new growth industry?". The Economist. 2009-08-27. Retrieved 2009-08-30. 
  10. ^ Frequently Asked Questions about Biochar | International Biochar Initiative. Biochar-international.org (2013-04-19). Retrieved on 2013-06-01.
  11. ^ Ratner, Buddy D. (2004). Pyrolytic carbon. In Biomaterials science: an introduction to materials in medicine. Academic Press. p. 171-180. ISBN 0-12-582463-7. Google Book Search. Retrieved 7 July 2011.
  12. ^ Evans, G. "Liquid Transport Biofuels – Technology Status Report", "National Non-Food Crops Centre", 14-04-08. Retrieved on 2009-05-05.
  13. ^ a b "Pyrolysis and Other Thermal Processing". US DOE. Archived from the original on 2007-08-14. 
  14. ^ [1]
  15. ^ N.J. Themelis et al. "Energy and Economic Value of Nonrecyclable Plastics and Municipal Solid Wastes that are Currently Landfilled in the Fifty States" Columbia University Earth Engineering Center
  16. ^ Middleton, Marc (2005-02-06). "Local recycler ignites Euro fuel market". Waste Management & Environment (Waste Management & Environment Media Pty Ltd.). Retrieved 2008-07-10. 
  17. ^ The Telegraph. "Pilot attempts first flight powered only by household plastic waste". 
  18. ^ Juan Daniel Martínez, Neus Puy, Ramón Murillo, Tomás García, María Victoria Navarro, Ana Maria Mastral, Waste tyre pyrolysis – A review, Renewable and Sustainable Energy Reviews, Volume 23, July 2013, Pages 179-213, ISSN 1364-0321, http://dx.doi.org/10.1016/j.rser.2013.02.038.
  19. ^ He, Fang; Weiming Yi; Xueyuan Bai (September 2006). "Investigation on caloric requirement of biomass pyrolysis using TG–DSC analyzer". Energy Conversion and Management 47 (15–16): 2461–2469. doi:10.1016/j.enconman.2005.11.011. 
  20. ^ Briens, Cedric; Berruti, Franco and Piskorz, Jan (2008). "Biomass Valorization for Fuel and Chemicals Production – A Review". International Journal of Chemical Reactor Engineering 6. doi:10.2202/1542-6580.1674. 
  21. ^ Bramer, E. A. and Brem, G. A new technology for fast pyrolysis of biomass: development of PyRos reactor. University of Twente
  22. ^ Bridgwater, A. V, Meier, D., & Radlein, D. (1999). An Overview of Fast Pyrolysis of Biomass. Organic Geochemistry, 30, 1479–1493.
  23. ^ "BTG Biomass Technology Group b.v. :: Technology:: Pyrolysis". Archived from the original on 2007-07-03. 
  24. ^ Jacqueline A. Campbell; McDougald, Graham; McNab, Hamish; Rees, Lovat; Tyas, Richard (2007). "Laboratory-scale synthesis of nitriles by catalyzed dehydration of amides and oximes under flash vacuum pyrolysis (FVP) conditions". Synthesis 20 (20): 3179–3184. doi:10.1055/s-2007-990782. 
  25. ^ "Biomass Feedstock for Slow Pyrolysis". BEST Pyrolysis, Inc. website. BEST Energies, Inc. Retrieved 2010-07-30. 
  26. ^ Marshall, A. T. & Morris, J. M. (2006) A Watery Solution and Sustainable Energy Parks, CIWM Journal, pp. 22–23
  27. ^ "Designer Fuels: The Next Fuel Generation" (PDF). Archived from the original on 2006-12-18. 
  28. ^ "Refining fast pyrolysis of biomass". Thermo-Chemical Conversion of Biomass (Thesis) (University of Twente). 2011. Retrieved 2012-05-30. 

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