Brewing

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https://en.wikipedia.org/wiki/Brewing 

A 16th-century brewery

Brewing is the production of beer by steeping a starch source (commonly cereal grains, the most popular of which is barley) in water and fermenting the resulting sweet liquid with yeast. It may be done in a brewery by a commercial brewer, at home by a homebrewer, or communally. Brewing has taken place since around the 6th millennium BC, and archaeological evidence suggests that emerging civilizations, including ancient Egypt, China, and Mesopotamia, brewed beer. Since the nineteenth century the brewing industry has been part of most western economies.

The basic ingredients of beer are water and a fermentable starch source such as malted barley. Most beer is fermented with a brewer's yeast and flavoured with hops. Less widely used starch sources include millet, sorghum and cassava. Secondary sources (adjuncts), such as maize (corn), rice, or sugar, may also be used, sometimes to reduce cost, or to add a feature, such as adding wheat to aid in retaining the foamy head of the beer. The most common starch source is ground cereal or "grist" – the proportion of the starch or cereal ingredients in a beer recipe may be called grist, grain bill, or simply mash ingredients.

Steps in the brewing process include malting, milling, mashing, lautering, boiling, fermenting, conditioning, filtering, and packaging. There are three main fermentation methods: warm, cool and spontaneous. Fermentation may take place in an open or closed fermenting vessel; a secondary fermentation may also occur in the cask or bottle. There are several additional brewing methods, such as Burtonisation, double dropping, and Yorkshire Square, as well as post-fermentation treatment such as filtering, and barrel-ageing.

History

Further information: History of beer and Women in brewing

The Alulu beer receipt records a purchase of "best" beer from a brewer, c. 2050 BC, from the Sumerian city of Umma in Mesopotamia (ancient Iraq).

See also: Fermentation in food processing § Brewing and winemaking

Brewing has taken place since around the 6th millennium BC, and archaeological evidence suggests emerging civilizations including China, ancient Egypt, and Mesopotamia brewed beer. Descriptions of various beer recipes can be found in cuneiform (the oldest known writing) from ancient Mesopotamia. In Mesopotamia the brewer's craft was the only profession which derived social sanction and divine protection from female deities/goddesses, specifically: Ninkasi, who covered the production of beer, Siris, who was used in a metonymic way to refer to beer, and Siduri, who covered the enjoyment of beer. In pre-industrial times, and in developing countries, women are frequently the main brewers.

As almost any cereal containing certain sugars can undergo spontaneous fermentation due to wild yeasts in the air, it is possible that beer-like beverages were independently developed throughout the world soon after a tribe or culture had domesticated cereal. Chemical tests of ancient pottery jars reveal that beer was produced as far back as about 7,000 years ago in what is today Iran. This discovery reveals one of the earliest known uses of fermentation and is the earliest evidence of brewing to date. In Mesopotamia, the oldest evidence of beer is believed to be a 6,000-year-old Sumerian tablet depicting people drinking a beverage through reed straws from a communal bowl. A 3900-year-old Sumerian poem honouring Ninkasi, the patron goddess of brewing, contains the oldest surviving beer recipe, describing the production of beer from barley via bread. The invention of bread and beer has been argued to be responsible for humanity's ability to develop technology and build civilization. The earliest chemically confirmed barley beer to date was discovered at Godin Tepe in the central Zagros Mountains of Iran, where fragments of a jug, at least 5,000 years old was found to be coated with beerstone, a by-product of the brewing process. Beer may have been known in Neolithic Europe as far back as 5,000 years ago, and was mainly brewed on a domestic scale.

Ale produced before the Industrial Revolution continued to be made and sold on a domestic scale, although by the 7th century AD beer was also being produced and sold by European monasteries. During the Industrial Revolution, the production of beer moved from artisanal manufacture to industrial manufacture, and domestic manufacture ceased to be significant by the end of the 19th century. The development of hydrometers and thermometers changed brewing by allowing the brewer more control of the process, and greater knowledge of the results. Today, the brewing industry is a global business, consisting of several dominant multinational companies and many thousands of smaller producers ranging from brewpubs to regional breweries. More than 133 billion litres (35 billion gallons) are sold per year—producing total global revenues of $294.5 billion (£147.7 billion) in 2006.

Ingredients

Malted barley before kilning or roasting

The basic ingredients of beer are water; a starch source, such as malted barley, able to be fermented (converted into alcohol); a brewer's yeast to produce the fermentation; and a flavouring, such as hops, to offset the sweetness of the malt. A mixture of starch sources may be used, with a secondary saccharide, such as maize (corn), rice, or sugar, these often being termed adjuncts, especially when used as a lower-cost substitute for malted barley. Less widely used starch sources include millet, sorghum, and cassava root in Africa, potato in Brazil, and agave in Mexico, among others. The most common starch source is ground cereal or "grist" – the proportion of the starch or cereal ingredients in a beer recipe may be called grist, grain bill, or simply mash ingredients.

Water

Beer is composed mostly of water. Regions have water with different mineral components; as a result, different regions were originally better suited to making certain types of beer, thus giving them a regional character. For example, Dublin has hard water well suited to making stout, such as Guinness; while Pilsen has soft water well suited to making pale lager, such as Pilsner Urquell. The waters of Burton in England contain gypsum, which benefits making pale ale to such a degree that brewers of pale ales will add gypsum to the local water in a process known as Burtonisation.

Starch source

Main articles: Malt and Mash ingredients

The starch source in a beer provides the fermentable material and is a key determinant of the strength and flavour of the beer. The most common starch source used in beer is malted grain. Grain is malted by soaking it in water, allowing it to begin germination, and then drying the partially germinated grain in a kiln. Malting grain produces enzymes that will allow conversion from starches in the grain into fermentable sugars during the mash process. Different roasting times and temperatures are used to produce different colours of malt from the same grain. Darker malts will produce darker beers.

Nearly all beer includes barley malt as the majority of the starch. This is because of its fibrous husk, which is important not only in the sparging stage of brewing (in which water is washed over the mashed barley grains to form the wort) but also as a rich source of amylase, a digestive enzyme that facilitates conversion of starch into sugars. Other malted and unmalted grains (including wheat, rice, oats, and rye, and, less frequently, maize (corn) and sorghum) may be used. In recent years, a few brewers have produced gluten-free beer made with sorghum with no barley malt for people who cannot digest gluten-containing grains like wheat, barley, and rye.

Hops

Main article: Hops

Hop cone grown in a hop field, Hallertau, Germany

Hops are the female flower clusters or seed cones of the hop vine Humulus lupulus, which are used as a flavouring and preservative agent in nearly all beer made today. Hops had been used for medicinal and food flavouring purposes since Roman times; by the 7th century in Carolingian monasteries in what is now Germany, beer was being made with hops, though it isn't until the thirteenth century that widespread cultivation of hops for use in beer is recorded. Before the thirteenth century, beer was flavoured with plants such as yarrow, wild rosemary, and bog myrtle, and other ingredients such as juniper berries, aniseed and ginger, which would be combined into a mixture known as gruit and used as hops are now used; between the thirteenth and the sixteenth century, during which hops took over as the dominant flavouring, beer flavoured with gruit was known as ale, while beer flavoured with hops was known as beer. Some beers today, such as Fraoch by the Scottish Heather Ales company and Cervoise Lancelot by the French Brasserie-Lancelot company, use plants other than hops for flavouring.

Hops contain several characteristics that brewers desire in beer: they contribute a bitterness that balances the sweetness of the malt; they provide floral, citrus, and herbal aromas and flavours; they have an antibiotic effect that favours the activity of brewer's yeast over less desirable microorganisms; and they aid in "head retention", the length of time that the foam on top of the beer (the beer head) will last. The preservative in hops comes from the lupulin glands which contain soft resins with alpha and beta acids. Though much studied, the preservative nature of the soft resins is not yet fully understood, though it has been observed that unless stored at a cool temperature, the preservative nature will decrease. Brewing is the sole major commercial use of hops.

Yeast

Main articles: Brewer's yeast, Saccharomyces cerevisiae, and Saccharomyces pastorianus

Yeast is the microorganism that is responsible for fermentation in beer. Yeast metabolises the sugars extracted from grains, which produces alcohol and carbon dioxide, and thereby turns wort into beer. In addition to fermenting the beer, yeast influences the character and flavour. The dominant types of yeast used to make beer are Saccharomyces cerevisiae, known as ale yeast, and Saccharomyces pastorianus, known as lager yeast; Brettanomyces ferments lambics, and Torulaspora delbrueckii ferments Bavarian weissbier. Before the role of yeast in fermentation was understood, fermentation involved wild or airborne yeasts, and a few styles such as lambics still use this method today. Emil Christian Hansen, a Danish biochemist employed by the Carlsberg Laboratory, developed pure yeast cultures which were introduced into the Carlsberg brewery in 1883, and pure yeast strains are now the main fermenting source used worldwide.

Clarifying agent

Main article: Finings

Some brewers add one or more clarifying agents to beer, which typically precipitate (collect as a solid) out of the beer along with protein solids and are found only in trace amounts in the finished product. This process makes the beer appear bright and clean, rather than the cloudy appearance of ethnic and older styles of beer such as wheat beers.

Examples of clarifying agents include isinglass, obtained from swim bladders of fish; Irish moss, a seaweed; kappa carrageenan, from the seaweed kappaphycus; polyclar (a commercial brand of clarifier); and gelatin. If a beer is marked "suitable for Vegans", it was generally clarified either with seaweed or with artificial agents, although the "Fast Cask" method invented by Marston's in 2009 may provide another method.

Brewing process

A clickable diagram depicting the process of brewing beer

Hot water tank

Mash tun

Malt

Hops

Copper

Hopback

Add yeast to
fermenter

Heat
exchanger

Bottling

Cask or keg

There are several steps in the brewing process, which may include malting, mashing, lautering, boiling, fermenting, conditioning, filtering, and packaging. The brewing equipment needed to make beer has grown more sophisticated over time, and now covers most aspects of the brewing process.

Malting is the process where barley grain is made ready for brewing. Malting is broken down into three steps in order to help to release the starches in the barley. First, during steeping, the grain is added to a vat with water and allowed to soak for approximately 40 hours. During germination, the grain is spread out on the floor of the germination room for around 5 days. The final part of malting is kilning when the malt goes through a very high temperature drying in a kiln; with gradual temperature increase over several hours. When kilning is complete, the grains are now termed malt, and they will be milled or crushed to break apart the kernels and expose the cotyledon, which contains the majority of the carbohydrates and sugars; this makes it easier to extract the sugars during mashing.

Mashing converts the starches released during the malting stage into sugars that can be fermented. The milled grain is mixed with hot water in a large vessel known as a mash tun. In this vessel, the grain and water are mixed together to create a cereal mash. During the mash, naturally occurring enzymes present in the malt convert the starches (long chain carbohydrates) in the grain into smaller molecules or simple sugars (mono-, di-, and tri-saccharides). This "conversion" is called saccharification which occurs between the temperatures 60–70 °C (140–158 °F). The result of the mashing process is a sugar-rich liquid or "wort", which is then strained through the bottom of the mash tun in a process known as lautering. Prior to lautering, the mash temperature may be raised to about 75–78 °C (167–172 °F) (known as a mashout) to free up more starch and reduce mash viscosity. Additional water may be sprinkled on the grains to extract additional sugars (a process known as sparging).

The wort is moved into a large tank known as a "copper" or kettle where it is boiled with hops and sometimes other ingredients such as herbs or sugars. This stage is where many chemical reactions take place, and where important decisions about the flavour, colour, and aroma of the beer are made. The boiling process serves to terminate enzymatic processes, precipitate proteins, isomerize hop resins, and concentrate and sterilize the wort. Hops add flavour, aroma and bitterness to the beer. At the end of the boil, the hopped wort settles to clarify in a vessel called a "whirlpool", where the more solid particles in the wort are separated out.

After the whirlpool, the wort is drawn away from the compacted hop trub, and rapidly cooled via a heat exchanger to a temperature where yeast can be added. A variety of heat exchanger designs are used in breweries, with the most common a plate-style. Water or glycol run in channels in the opposite direction of the wort, causing a rapid drop in temperature. It is very important to quickly cool the wort to a level where yeast can be added safely as yeast is unable to grow in very high temperatures, and will start to die in temperatures above 60 °C (140 °F). After the wort goes through the heat exchanger, the cooled wort goes into a fermentation tank. A type of yeast is selected and added, or "pitched", to the fermentation tank. When the yeast is added to the wort, the fermenting process begins, where the sugars turn into alcohol, carbon dioxide and other components. When the fermentation is complete the brewer may rack the beer into a new tank, called a conditioning tank. Conditioning of the beer is the process in which the beer ages, the flavour becomes smoother, and flavours that are unwanted dissipate. After conditioning for a week to several months, the beer may be filtered and force carbonated for bottling, or fined in the cask.

Mashing

Main article: Mashing

A mash tun at the Bass Museum in Burton-upon-Trent

Mashing is the process of combining a mix of milled grain (typically malted barley with supplementary grains such as corn, sorghum, rye or wheat), known as the "grist" or "grain bill", and water, known as "liquor", and heating this mixture in a vessel called a "mash tun". Mashing is a form of steeping, and defines the act of brewing, such as with making tea, sake, and soy sauce. Technically, wine, cider and mead are not brewed but rather vinified, as there is no steeping process involving solids. Mashing allows the enzymes in the malt to break down the starch in the grain into sugars, typically maltose to create a malty liquid called wort. There are two main methods – infusion mashing, in which the grains are heated in one vessel; and decoction mashing, in which a proportion of the grains are boiled and then returned to the mash, raising the temperature. Mashing involves pauses at certain temperatures (notably 45–62–73 °C or 113–144–163 °F), and takes place in a "mash tun" – an insulated brewing vessel with a false bottom. The end product of mashing is called a "mash".

Mashing usually takes 1 to 2 hours, and during this time the various temperature rests activate different enzymes depending upon the type of malt being used, its modification level, and the intention of the brewer. The activity of these enzymes convert the starches of the grains to dextrins and then to fermentable sugars such as maltose. A mash rest from 49–55 °C (120–131 °F) activates various proteases, which break down proteins that might otherwise cause the beer to be hazy. This rest is generally used only with undermodified (i.e. undermalted) malts which are decreasingly popular in Germany and the Czech Republic, or non-malted grains such as corn and rice, which are widely used in North American beers. A mash rest at 60 °C (140 °F) activates β-glucanase, which breaks down gummy β-glucans in the mash, making the sugars flow out more freely later in the process. In the modern mashing process, commercial fungal based β-glucanase may be added as a supplement. Finally, a mash rest temperature of 65–71 °C (149–160 °F) is used to convert the starches in the malt to sugar, which is then usable by the yeast later in the brewing process. Doing the latter rest at the lower end of the range favours β-amylase enzymes, producing more low-order sugars like maltotriose, maltose, and glucose which are more fermentable by the yeast. This in turn creates a beer lower in body and higher in alcohol. A rest closer to the higher end of the range favours α-amylase enzymes, creating more higher-order sugars and dextrins which are less fermentable by the yeast, so a fuller-bodied beer with less alcohol is the result. Duration and pH variances also affect the sugar composition of the resulting wort.

Lautering

Lauter tun

Main article: Lautering

Lautering is the separation of the wort (the liquid containing the sugar extracted during mashing) from the grains. This is done either in a mash tun outfitted with a false bottom, in a lauter tun, or in a mash filter. Most separation processes have two stages: first wort run-off, during which the extract is separated in an undiluted state from the spent grains, and sparging, in which extract which remains with the grains is rinsed off with hot water. The lauter tun is a tank with holes in the bottom small enough to hold back the large bits of grist and hulls (the ground or milled cereal). The bed of grist that settles on it is the actual filter. Some lauter tuns have provision for rotating rakes or knives to cut into the bed of grist to maintain good flow. The knives can be turned so they push the grain, a feature used to drive the spent grain out of the vessel. The mash filter is a plate-and-frame filter. The empty frames contain the mash, including the spent grains, and have a capacity of around one hectoliter. The plates contain a support structure for the filter cloth. The plates, frames, and filter cloths are arranged in a carrier frame like so: frame, cloth, plate, cloth, with plates at each end of the structure. Newer mash filters have bladders that can press the liquid out of the grains between spargings. The grain does not act like a filtration medium in a mash filter.

Boiling

After mashing, the beer wort is boiled with hops (and other flavourings if used) in a large tank known as a "copper" or brew kettle – though historically the mash vessel was used and is still in some small breweries. The boiling process is where chemical reactions take place, including sterilization of the wort to remove unwanted bacteria, releasing of hop flavours, bitterness and aroma compounds through isomerization, stopping of enzymatic processes, precipitation of proteins, and concentration of the wort. Finally, the vapours produced during the boil volatilise off-flavours, including dimethyl sulfide precursors. The boil is conducted so that it is even and intense – a continuous "rolling boil". The boil on average lasts between 45 and 90 minutes, depending on its intensity, the hop addition schedule, and volume of water the brewer expects to evaporate. At the end of the boil, solid particles in the hopped wort are separated out, usually in a vessel called a "whirlpool".

Brew kettle or copper

Brew kettles at Brasserie La Choulette in France

Copper is the traditional material for the boiling vessel for two main reasons: firstly because copper transfers heat quickly and evenly; secondly because the bubbles produced during boiling, which could act as an insulator against the heat, do not cling to the surface of copper, so the wort is heated in a consistent manner. The simplest boil kettles are direct-fired, with a burner underneath. These can produce a vigorous and favourable boil, but are also apt to scorch the wort where the flame touches the kettle, causing caramelisation and making cleanup difficult. Most breweries use a steam-fired kettle, which uses steam jackets in the kettle to boil the wort. Breweries usually have a boiling unit either inside or outside of the kettle, usually a tall, thin cylinder with vertical tubes, called a calandria, through which wort is pumped.

Whirlpool

At the end of the boil, solid particles in the hopped wort are separated out, usually in a vessel called a "whirlpool" or "settling tank". The whirlpool was devised by Henry Ranulph Hudston while working for the Molson Brewery in 1960 to utilise the so-called tea leaf paradox to force the denser solids known as "trub" (coagulated proteins, vegetable matter from hops) into a cone in the centre of the whirlpool tank. Whirlpool systems vary: smaller breweries tend to use the brew kettle, larger breweries use a separate tank, and design will differ, with tank floors either flat, sloped, conical or with a cup in the centre. The principle in all is that by swirling the wort the centripetal force will push the trub into a cone at the centre of the bottom of the tank, where it can be easily removed.

Hopback

A hopback is a traditional additional chamber that acts as a sieve or filter by using whole hops to clear debris (or "trub") from the unfermented (or "green") wort, as the whirlpool does, and also to increase hop aroma in the finished beer. It is a chamber between the brewing kettle and wort chiller. Hops are added to the chamber, the hot wort from the kettle is run through it, and then immediately cooled in the wort chiller before entering the fermentation chamber. Hopbacks utilizing a sealed chamber facilitate maximum retention of volatile hop aroma compounds that would normally be driven off when the hops contact the hot wort. While a hopback has a similar filtering effect as a whirlpool, it operates differently: a whirlpool uses centrifugal forces, a hopback uses a layer of whole hops to act as a filter bed. Furthermore, while a whirlpool is useful only for the removal of pelleted hops (as flowers do not tend to separate as easily), in general hopbacks are used only for the removal of whole flower hops (as the particles left by pellets tend to make it through the hopback). The hopback has mainly been substituted in modern breweries by the whirlpool.

Wort cooling

After the whirlpool, the wort must be brought down to fermentation temperatures 20–26 °C (68–79 °F) before yeast is added. In modern breweries this is achieved through a plate heat exchanger. A plate heat exchanger has sereral ridged plates, which form two separate paths. The wort is pumped into the heat exchanger, and goes through every other gap between the plates. The cooling medium, usually water from a cold liquor tank, goes through the other gaps. The ridges in the plates ensure turbulent flow. A good heat exchanger can drop 95 °C (203 °F) wort to 20 °C (68 °F) while warming the cooling medium from about 10 °C (50 °F) to 80 °C (176 °F). The last few plates often use a cooling medium which can be cooled to below the freezing point, which allows a finer control over the wort-out temperature, and also enables cooling to around 10 °C (50 °F). After cooling, oxygen is often dissolved into the wort to revitalize the yeast and aid its reproduction.

While boiling, it is useful to recover some of the energy used to boil the wort. On its way out of the brewery, the steam created during the boil is passed over a coil through which unheated water flows. By adjusting the rate of flow, the output temperature of the water can be controlled. This is also often done using a plate heat exchanger. The water is then stored for later use in the next mash, in equipment cleaning, or wherever necessary. Another common method of energy recovery takes place during the wort cooling. When cold water is used to cool the wort in a heat exchanger, the water is significantly warmed. In an efficient brewery, cold water is passed through the heat exchanger at a rate set to maximize the water's temperature upon exiting. This now-hot water is then stored in a hot water tank.

Fermenting

Modern closed fermentation vessels

Fermentation takes place in fermentation vessels which come in various forms, from enormous cylindroconical vessels, through open stone vessels, to wooden vats. After the wort is cooled and aerated – usually with sterile air – yeast is added to it, and it begins to ferment. It is during this stage that sugars won from the malt are converted into alcohol and carbon dioxide, and the product can be called beer for the first time.

Most breweries today use cylindroconical vessels, or CCVs, which have a conical bottom and a cylindrical top. The cone's angle is typically around 60°, an angle that will allow the yeast to flow towards the cone's apex, but is not so steep as to take up too much vertical space. CCVs can handle both fermenting and conditioning in the same tank. At the end of fermentation, the yeast and other solids which have fallen to the cone's apex can be simply flushed out of a port at the apex. Open fermentation vessels are also used, often for show in brewpubs, and in Europe in wheat beer fermentation. These vessels have no tops, which makes harvesting top-fermenting yeasts very easy. The open tops of the vessels make the risk of infection greater, but with proper cleaning procedures and careful protocol about who enters fermentation chambers, the risk can be well controlled. Fermentation tanks are typically made of stainless steel. If they are simple cylindrical tanks with beveled ends, they are arranged vertically, as opposed to conditioning tanks which are usually laid out horizontally. Only a very few breweries still use wooden vats for fermentation as wood is difficult to keep clean and infection-free and must be repitched more or less yearly.

Fermentation methods

See also: Beer style

Open vessels showing fermentation taking place

There are three main fermentation methods, warm, cool, and wild or spontaneous. Fermentation may take place in open or closed vessels. There may be a secondary fermentation which can take place in the brewery, in the cask or in the bottle.

Brewing yeasts are traditionally classed as "top-cropping" (or "top-fermenting") and "bottom-cropping" (or "bottom-fermenting"); the yeasts classed as top-fermenting are generally used in warm fermentations, where they ferment quickly, and the yeasts classed as bottom-fermenting are used in cooler fermentations where they ferment more slowly. Yeast were termed top or bottom cropping, because the yeast was collected from the top or bottom of the fermenting wort to be reused for the next brew. This terminology is somewhat inappropriate in the modern era; after the widespread application of brewing mycology it was discovered that the two separate collecting methods involved two different yeast species that favoured different temperature regimes, namely Saccharomyces cerevisiae in top-cropping at warmer temperatures and Saccharomyces pastorianus in bottom-cropping at cooler temperatures. As brewing methods changed in the 20th century, cylindro-conical fermenting vessels became the norm and the collection of yeast for both Saccharomyces species is done from the bottom of the fermenter. Thus the method of collection no longer implies a species association. There are a few remaining breweries who collect yeast in the top-cropping method, such as Samuel Smiths brewery in Yorkshire, Marstons in Staffordshire and several German hefeweizen producers.

For both types, yeast is fully distributed through the beer while it is fermenting, and both equally flocculate (clump together and precipitate to the bottom of the vessel) when fermentation is finished. By no means do all top-cropping yeasts demonstrate this behaviour, but it features strongly in many English yeasts that may also exhibit chain forming (the failure of budded cells to break from the mother cell), which is in the technical sense different from true flocculation. The most common top-cropping brewer's yeast, Saccharomyces cerevisiae, is the same species as the common baking yeast. However, baking and brewing yeasts typically belong to different strains, cultivated to favour different characteristics: baking yeast strains are more aggressive, in order to carbonate dough in the shortest amount of time; brewing yeast strains act slower, but tend to tolerate higher alcohol concentrations (normally 12–15% abv is the maximum, though under special treatment some ethanol-tolerant strains can be coaxed up to around 20%). Modern quantitative genomics has revealed the complexity of Saccharomyces species to the extent that yeasts involved in beer and wine production commonly involve hybrids of so-called pure species. As such, the yeasts involved in what has been typically called top-cropping or top-fermenting ale may be both Saccharomyces cerevisiae and complex hybrids of Saccharomyces cerevisiae and Saccharomyces kudriavzevii. Three notable ales, Chimay, Orval and Westmalle, are fermented with these hybrid strains, which are identical to wine yeasts from Switzerland.

Warm fermentation

In general, yeasts such as Saccharomyces cerevisiae are fermented at warm temperatures between 15 and 20 °C (59 and 68 °F), occasionally as high as 24 °C (75 °F), while the yeast used by Brasserie Dupont for saison ferments even higher at 29 to 35 °C (84 to 95 °F). They generally form a foam on the surface of the fermenting beer, which is called barm, as during the fermentation process its hydrophobic surface causes the flocs to adhere to CO₂ and rise; because of this, they are often referred to as "top-cropping" or "top-fermenting" – though this distinction is less clear in modern brewing with the use of cylindro-conical tanks. Generally, warm-fermented beers, which are usually termed ale, are ready to drink within three weeks after the beginning of fermentation, although some brewers will condition or mature them for several months.

Cool fermentation

Main article: Lager

When a beer has been brewed using a cool fermentation of around 10 °C (50 °F), compared to typical warm fermentation temperatures of 18 °C (64 °F), then stored (or lagered) for typically several weeks (or months) at temperatures close to freezing point, it is termed a "lager". During the lagering or storage phase several flavour components developed during fermentation dissipate, resulting in a "cleaner" flavour. Though it is the slow, cool fermentation and cold conditioning (or lagering) that defines the character of lager, the main technical difference is with the yeast generally used, which is Saccharomyces pastorianus. Technical differences include the ability of lager yeast to metabolize melibiose, and the tendency to settle at the bottom of the fermenter (though ale yeasts can also become bottom settling by selection); though these technical differences are not considered by scientists to be influential in the character or flavour of the finished beer, brewers feel otherwise – sometimes cultivating their own yeast strains which may suit their brewing equipment or for a particular purpose, such as brewing beers with a high abv.

Spontaneous fermentation at Timmermans in Belgium

Brewers in Bavaria had for centuries been selecting cold-fermenting yeasts by storing ("lagern") their beers in cold alpine caves. The process of natural selection meant that the wild yeasts that were most cold tolerant would be the ones that would remain actively fermenting in the beer that was stored in the caves. A sample of these Bavarian yeasts was sent from the Spaten brewery in Munich to the Carlsberg brewery in Copenhagen in 1845 who began brewing with it. In 1883 Emile Hansen completed a study on pure yeast culture isolation and the pure strain obtained from Spaten went into industrial production in 1884 as Carlsberg yeast No 1. Another specialized pure yeast production plant was installed at the Heineken Brewery in Rotterdam the following year and together they began the supply of pure cultured yeast to brewers across Europe. This yeast strain was originally classified as Saccharomyces carlsbergensis, a now defunct species name which has been superseded by the currently accepted taxonomic classification Saccharomyces pastorianus.

Spontaneous fermentation

Lambic beers are historically brewed in Brussels and the nearby Pajottenland region of Belgium without any yeast inoculation. The wort is cooled in open vats (called "coolships"), where the yeasts and microbiota present in the brewery (such as Brettanomyces) are allowed to settle to create a spontaneous fermentation, and are then conditioned or matured in oak barrels for typically one to three years.

Conditioning

Conditioning tanks at Anchor Brewing Company

After an initial or primary fermentation, beer is conditioned, matured or aged, in one of several ways, which can take from 2 to 4 weeks, several months, or several years, depending on the brewer's intention for the beer. The beer is usually transferred into a second container, so that it is no longer exposed to the dead yeast and other debris (also known as "trub") that have settled to the bottom of the primary fermenter. This prevents the formation of unwanted flavours and harmful compounds such as acetaldehyde.

Kräusening

Kräusening (pronounced KROY-zen-ing) is a conditioning method in which fermenting wort is added to the finished beer. The active yeast will restart fermentation in the finished beer, and so introduce fresh carbon dioxide; the conditioning tank will be then sealed so that the carbon dioxide is dissolved into the beer producing a lively "condition" or level of carbonation. The kräusening method may also be used to condition bottled beer.

Lagering

Lagers are stored at cellar temperature or below for 1–6 months while still on the yeast. The process of storing, or conditioning, or maturing, or aging a beer at a low temperature for a long period is called "lagering", and while it is associated with lagers, the process may also be done with ales, with the same result – that of cleaning up various chemicals, acids and compounds.

Secondary fermentation

During secondary fermentation, most of the remaining yeast will settle to the bottom of the second fermenter, yielding a less hazy product.

Bottle fermentation

Some beers undergo an additional fermentation in the bottle giving natural carbonation. This may be a second and/or third fermentation. They are bottled with a viable yeast population in suspension. If there is no residual fermentable sugar left, sugar or wort or both may be added in a process known as priming. The resulting fermentation generates CO₂ that is trapped in the bottle, remaining in solution and providing natural carbonation. Bottle-conditioned beers may be either filled unfiltered direct from the fermentation or conditioning tank, or filtered and then reseeded with yeast.

Cask conditioning

Cask ales with gravity dispense at a beer festival

Cask ale (or cask-conditioned beer) is unfiltered, unpasteurised beer that is conditioned by a secondary fermentation in a metal, plastic or wooden cask. It is dispensed from the cask by being either poured from a tap by gravity, or pumped up from a cellar via a beer engine (hand pump). Sometimes a cask breather is used to keep the beer fresh by allowing carbon dioxide to replace oxygen as the beer is drawn off the cask. Until 2018, the Campaign for Real Ale (CAMRA) defined real ale as beer "served without the use of extraneous carbon dioxide", which would disallow the use of a cask breather, a policy which was reversed in April 2018 to allow beer served with the use of cask breathers to meet its definition of real ale.

Barrel-ageing

Main article: Barrel-aged beer

Barrel-ageing (US: Barrel aging) is the process of ageing beer in wooden barrels to achieve a variety of effects in the final product. Sour beers such as lambics are fully fermented in wood, while other beers are aged in barrels which were previously used for maturing wines or spirits. In 2016 "Craft Beer and Brewing" wrote: "Barrel-aged beers are so trendy that nearly every taphouse and beer store has a section of them.

Filtering

Main article: Filtered beer

Diatomaceous earth, used to create a filtration bed

Filtering stabilises the flavour of beer, holding it at a point acceptable to the brewer, and preventing further development from the yeast, which under poor conditions can release negative components and flavours. Filtering also removes haze, clearing the beer, and so giving it a "polished shine and brilliance". Beer with a clear appearance has been commercially desirable for brewers since the development of glass vessels for storing and drinking beer, along with the commercial success of pale lager, which – due to the lagering process in which haze and particles settle to the bottom of the tank and so the beer "drops bright" (clears) – has a natural bright appearance and shine.

There are several forms of filters; they may be in the form of sheets or "candles", or they may be a fine powder such as diatomaceous earth (also called kieselguhr), which is added to the beer to form a filtration bed which allows liquid to pass, but holds onto suspended particles such as yeast. Filters range from rough filters that remove much of the yeast and any solids (e.g., hops, grain particles) left in the beer, to filters tight enough to strain colour and body from the beer. Filtration ratings are divided into rough, fine, and sterile. Rough filtration leaves some cloudiness in the beer, but it is noticeably clearer than unfiltered beer. Fine filtration removes almost all cloudiness. Sterile filtration removes almost all microorganisms.

Sheet (pad) filters

These filters use sheets that allow only particles smaller than a given size to pass through. The sheets are placed into a filtering frame, sanitized (with boiling water, for example) and then used to filter the beer. The sheets can be flushed if the filter becomes blocked. The sheets are usually disposable and are replaced between filtration sessions. Often the sheets contain powdered filtration media to aid in filtration.

Pre-made filters have two sides. One with loose holes, and the other with tight holes. Flow goes from the side with loose holes to the side with the tight holes, with the intent that large particles get stuck in the large holes while leaving enough room around the particles and filter medium for smaller particles to go through and get stuck in tighter holes.

Sheets are sold in nominal ratings, and typically 90% of particles larger than the nominal rating are caught by the sheet.

Kieselguhr filters

Filters that use a powder medium are considerably more complicated to operate, but can filter much more beer before regeneration. Common media include diatomaceous earth and perlite.

By-products

Spent grain, a brewing by-product

Brewing by-products are "spent grain" and the sediment (or "dregs") from the filtration process which may be dried and resold as "brewers dried yeast" for poultry feed, or made into yeast extract which is used in brands such as Vegemite and Marmite. The process of turning the yeast sediment into edible yeast extract was discovered by German scientist Justus von Liebig.

Brewer's spent grain (also called spent grain, brewer's grain or draff) is the main by-product of the brewing process; it consists of the residue of malt and grain which remains in the lauter tun after the lautering process. It consists primarily of grain husks, pericarp, and fragments of endosperm. As it mainly consists of carbohydrates and proteins, and is readily consumed by animals, spent grain is used in animal feed. Spent grains can also be used as fertilizer, whole grains in bread, as well as in the production of flour and biogas. Spent grain is also an ideal medium for growing mushrooms, such as shiitake, and some breweries are already either growing their own mushrooms or supplying spent grain to mushroom farms. Spent grains can be used in the production of red bricks, to improve the open porosity and reduce thermal conductivity of the ceramic mass.

Brewing industry

The brewing industry is a global business, consisting of several dominant multinational companies and many thousands of other producers known as microbreweries or regional breweries or craft breweries depending on size, region, and marketing preference. More than 133 billion liters (3.5×10¹⁰ U.S. gallons; 2.9×10¹⁰ imperial gallons) are sold per year—producing total global revenues of $294.5 billion (£147.7 billion) as of 2006. SABMiller became the largest brewing company in the world when it acquired Royal Grolsch, brewer of Dutch premium beer brand Grolsch. InBev was the second-largest beer-producing company in the world and Anheuser-Busch held the third spot, but after the acquisition of Anheuser-Busch by InBev, the new Anheuser-Busch InBev company is currently the largest brewer in the world.

Brewing at home is subject to regulation and prohibition in many countries. Restrictions on homebrewing were lifted in the UK in 1963, Australia followed suit in 1972, and the US in 1978, though individual states were allowed to pass their own laws limiting production.

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:

• Carbonization, the complete pyrolysis of organic matter, which usually leaves a solid residue that consists mostly of elemental carbon.
• Methane pyrolysis, the direct conversion of methane to hydrogen fuel and separable solid carbon, sometimes using molten metal catalysts.
• Hydrous pyrolysis, in the presence of superheated water or steam, producing hydrogen and substantial atmospheric carbon dioxide.
• Dry distillation, as in the original production of sulfuric acid from sulfates.
• Destructive distillation, as in the manufacture of charcoal, coke and activated carbon.
  • Charcoal burning, the production of charcoal.
  • Tar production by destructive distillation of wood in tar kilns.
• Caramelization of sugars.
• High-temperature cooking processes such as roasting, frying, toasting, and grilling.
• Cracking of heavier hydrocarbons into lighter ones, as in oil refining.
• Thermal depolymerization, which breaks down plastics and other polymers into monomers and oligomers.
• Ceramization involving the formation of polymer derived ceramics from preceramic polymers under an inert atmosphere.
• Catagenesis, the natural conversion of buried organic matter to fossil fuels.
• Flash vacuum pyrolysis, used in organic synthesis.

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

See also: Clandestine chemistry § Pyrolysis

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

Cooking

Caramelized onions are slightly pyrolyzed.

 

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

See also: Biofuel

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

See also: Thermal depolymerization

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

See also: 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
₂H
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.