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Wednesday, December 1, 2021

Fuel cell

    From Wikipedia, the free encyclopedia

    Demonstration model of a direct-methanol fuel cell (black layered cube) in its enclosure.
    Scheme of a proton-conducting fuel cell

    A fuel cell is an electrochemical cell that converts the chemical energy of a fuel (often hydrogen) and an oxidizing agent (often oxygen) into electricity through a pair of redox reactions. Fuel cells are different from most batteries in requiring a continuous source of fuel and oxygen (usually from air) to sustain the chemical reaction, whereas in a battery the chemical energy usually comes from metals and their ions or oxides that are commonly already present in the battery, except in flow batteries. Fuel cells can produce electricity continuously for as long as fuel and oxygen are supplied.

    The first fuel cells were invented by Sir William Grove in 1838. The first commercial use of fuel cells came more than a century later following the invention of the hydrogen–oxygen fuel cell by Francis Thomas Bacon in 1932. The alkaline fuel cell, also known as the Bacon fuel cell after its inventor, has been used in NASA space programs since the mid-1960s to generate power for satellites and space capsules. Since then, fuel cells have been used in many other applications. Fuel cells are used for primary and backup power for commercial, industrial and residential buildings and in remote or inaccessible areas. They are also used to power fuel cell vehicles, including forklifts, automobiles, buses, boats, motorcycles and submarines.

    There are many types of fuel cells, but they all consist of an anode, a cathode, and an electrolyte that allows ions, often positively charged hydrogen ions (protons), to move between the two sides of the fuel cell. At the anode a catalyst causes the fuel to undergo oxidation reactions that generate ions (often positively charged hydrogen ions) and electrons. The ions move from the anode to the cathode through the electrolyte. At the same time, electrons flow from the anode to the cathode through an external circuit, producing direct current electricity. At the cathode, another catalyst causes ions, electrons, and oxygen to react, forming water and possibly other products. Fuel cells are classified by the type of electrolyte they use and by the difference in startup time ranging from 1 second for proton-exchange membrane fuel cells (PEM fuel cells, or PEMFC) to 10 minutes for solid oxide fuel cells (SOFC). A related technology is flow batteries, in which the fuel can be regenerated by recharging. Individual fuel cells produce relatively small electrical potentials, about 0.7 volts, so cells are "stacked", or placed in series, to create sufficient voltage to meet an application's requirements. In addition to electricity, fuel cells produce water, heat and, depending on the fuel source, very small amounts of nitrogen dioxide and other emissions. The energy efficiency of a fuel cell is generally between 40 and 60%; however, if waste heat is captured in a cogeneration scheme, efficiencies of up to 85% can be obtained.

    History

    Sketch of Sir William Grove's 1839 fuel cell

    The first references to hydrogen fuel cells appeared in 1838. In a letter dated October 1838 but published in the December 1838 edition of The London and Edinburgh Philosophical Magazine and Journal of Science, Welsh physicist and barrister Sir William Grove wrote about the development of his first crude fuel cells. He used a combination of sheet iron, copper and porcelain plates, and a solution of sulphate of copper and dilute acid. In a letter to the same publication written in December 1838 but published in June 1839, German physicist Christian Friedrich Schönbein discussed the first crude fuel cell that he had invented. His letter discussed current generated from hydrogen and oxygen dissolved in water. Grove later sketched his design, in 1842, in the same journal. The fuel cell he made used similar materials to today's phosphoric acid fuel cell.

    In 1932, Francis Thomas Bacon invented a fuel cell which derived power from hydrogen and oxygen. This was used by NASA to power lights, air-conditioning and communications.

    The Brits who bolstered the Moon landings, BBC Archives.

    In 1932, English engineer Francis Thomas Bacon successfully developed a 5 kW stationary fuel cell. The alkaline fuel cell (AFC), also known as the Bacon fuel cell after its inventor, is one of the most developed fuel cell technologies, which NASA has used since the mid-1960s.

    In 1955, W. Thomas Grubb, a chemist working for the General Electric Company (GE), further modified the original fuel cell design by using a sulphonated polystyrene ion-exchange membrane as the electrolyte. Three years later another GE chemist, Leonard Niedrach, devised a way of depositing platinum onto the membrane, which served as catalyst for the necessary hydrogen oxidation and oxygen reduction reactions. This became known as the "Grubb-Niedrach fuel cell". GE went on to develop this technology with NASA and McDonnell Aircraft, leading to its use during Project Gemini. This was the first commercial use of a fuel cell. In 1959, a team led by Harry Ihrig built a 15 kW fuel cell tractor for Allis-Chalmers, which was demonstrated across the U.S. at state fairs. This system used potassium hydroxide as the electrolyte and compressed hydrogen and oxygen as the reactants. Later in 1959, Bacon and his colleagues demonstrated a practical five-kilowatt unit capable of powering a welding machine. In the 1960s, Pratt & Whitney licensed Bacon's U.S. patents for use in the U.S. space program to supply electricity and drinking water (hydrogen and oxygen being readily available from the spacecraft tanks). In 1991, the first hydrogen fuel cell automobile was developed by Roger Billings.

    UTC Power was the first company to manufacture and commercialize a large, stationary fuel cell system for use as a co-generation power plant in hospitals, universities and large office buildings.

    In recognition of the fuel cell industry and America's role in fuel cell development, the US Senate recognized 8 October 2015 as National Hydrogen and Fuel Cell Day, passing S. RES 217. The date was chosen in recognition of the atomic weight of hydrogen (1.008).

    Types of fuel cells; design

    Fuel cells come in many varieties; however, they all work in the same general manner. They are made up of three adjacent segments: the anode, the electrolyte, and the cathode. Two chemical reactions occur at the interfaces of the three different segments. The net result of the two reactions is that fuel is consumed, water or carbon dioxide is created, and an electric current is created, which can be used to power electrical devices, normally referred to as the load.

    At the anode a catalyst oxidizes the fuel, usually hydrogen, turning the fuel into a positively charged ion and a negatively charged electron. The electrolyte is a substance specifically designed so ions can pass through it, but the electrons cannot. The freed electrons travel through a wire creating the electric current. The ions travel through the electrolyte to the cathode. Once reaching the cathode, the ions are reunited with the electrons and the two react with a third chemical, usually oxygen, to create water or carbon dioxide.

    A block diagram of a fuel cell

    Design features in a fuel cell include:

    • The electrolyte substance, which usually defines the type of fuel cell, and can be made from a number of substances like potassium hydroxide, salt carbonates, and phosphoric acid.
    • The fuel that is used. The most common fuel is hydrogen.
    • The anode catalyst, usually fine platinum powder, breaks down the fuel into electrons and ions.
    • The cathode catalyst, often nickel, converts ions into waste chemicals, with water being the most common type of waste.
    • Gas diffusion layers that are designed to resist oxidization.

    A typical fuel cell produces a voltage from 0.6 to 0.7 V at full rated load. Voltage decreases as current increases, due to several factors:

    • Activation loss
    • Ohmic loss (voltage drop due to resistance of the cell components and interconnections)
    • Mass transport loss (depletion of reactants at catalyst sites under high loads, causing rapid loss of voltage).

    To deliver the desired amount of energy, the fuel cells can be combined in series to yield higher voltage, and in parallel to allow a higher current to be supplied. Such a design is called a fuel cell stack. The cell surface area can also be increased, to allow higher current from each cell.

    Proton-exchange membrane fuel cells (PEMFCs)

    Construction of a high-temperature PEMFC: Bipolar plate as electrode with in-milled gas channel structure, fabricated from conductive composites (enhanced with graphite, carbon black, carbon fiber, and/or carbon nanotubes for more conductivity); Porous carbon papers; reactive layer, usually on the polymer membrane applied; polymer membrane.
    Condensation of water produced by a PEMFC on the air channel wall. The gold wire around the cell ensures the collection of electric current.
     
    SEM micrograph of a PEMFC MEA cross-section with a non-precious metal catalyst cathode and Pt/C anode. False colors applied for clarity.

    In the archetypical hydrogen–oxide proton-exchange membrane fuel cell design, a proton-conducting polymer membrane (typically nafion) contains the electrolyte solution that separates the anode and cathode sides. This was called a solid polymer electrolyte fuel cell (SPEFC) in the early 1970s, before the proton-exchange mechanism was well understood. (Notice that the synonyms polymer electrolyte membrane and 'proton-exchange mechanism result in the same acronym.)

    On the anode side, hydrogen diffuses to the anode catalyst where it later dissociates into protons and electrons. These protons often react with oxidants causing them to become what are commonly referred to as multi-facilitated proton membranes. The protons are conducted through the membrane to the cathode, but the electrons are forced to travel in an external circuit (supplying power) because the membrane is electrically insulating. On the cathode catalyst, oxygen molecules react with the electrons (which have traveled through the external circuit) and protons to form water.

    In addition to this pure hydrogen type, there are hydrocarbon fuels for fuel cells, including diesel, methanol (see: direct-methanol fuel cells and indirect methanol fuel cells) and chemical hydrides. The waste products with these types of fuel are carbon dioxide and water. When hydrogen is used, the CO2 is released when methane from natural gas is combined with steam, in a process called steam methane reforming, to produce the hydrogen. This can take place in a different location to the fuel cell, potentially allowing the hydrogen fuel cell to be used indoors—for example, in fork lifts.

    The different components of a PEMFC are

    1. bipolar plates,
    2. electrodes,
    3. catalyst,
    4. membrane, and
    5. the necessary hardware such as current collectors and gaskets.

    The materials used for different parts of the fuel cells differ by type. The bipolar plates may be made of different types of materials, such as, metal, coated metal, graphite, flexible graphite, C–C composite, carbonpolymer composites etc. The membrane electrode assembly (MEA) is referred to as the heart of the PEMFC and is usually made of a proton-exchange membrane sandwiched between two catalyst-coated carbon papers. Platinum and/or similar type of noble metals are usually used as the catalyst for PEMFC, and these can be contaminated by carbon monoxide, necessitating a relatively pure hydrogen fuel. The electrolyte could be a polymer membrane.

    Proton-exchange membrane fuel cell design issues

    Cost
    In 2013, the Department of Energy estimated that 80-kW automotive fuel cell system costs of US$67 per kilowatt could be achieved, assuming volume production of 100,000 automotive units per year and US$55 per kilowatt could be achieved, assuming volume production of 500,000 units per year. Many companies are working on techniques to reduce cost in a variety of ways including reducing the amount of platinum needed in each individual cell. Ballard Power Systems has experimented with a catalyst enhanced with carbon silk, which allows a 30% reduction (1.0–0.7 mg/cm2) in platinum usage without reduction in performance. Monash University, Melbourne uses PEDOT as a cathode. A 2011-published study documented the first metal-free electrocatalyst using relatively inexpensive doped carbon nanotubes, which are less than 1% the cost of platinum and are of equal or superior performance. A recently published article demonstrated how the environmental burdens change when using carbon nanotubes as carbon substrate for platinum.
    Water and air management (in PEMFCs)
    In this type of fuel cell, the membrane must be hydrated, requiring water to be evaporated at precisely the same rate that it is produced. If water is evaporated too quickly, the membrane dries, resistance across it increases, and eventually it will crack, creating a gas "short circuit" where hydrogen and oxygen combine directly, generating heat that will damage the fuel cell. If the water is evaporated too slowly, the electrodes will flood, preventing the reactants from reaching the catalyst and stopping the reaction. Methods to manage water in cells are being developed like electroosmotic pumps focusing on flow control. Just as in a combustion engine, a steady ratio between the reactant and oxygen is necessary to keep the fuel cell operating efficiently.
    Temperature management
    The same temperature must be maintained throughout the cell in order to prevent destruction of the cell through thermal loading. This is particularly challenging as the 2H2 + O2 → 2H2O reaction is highly exothermic, so a large quantity of heat is generated within the fuel cell.
    Durability, service life, and special requirements for some type of cells
    Stationary fuel cell applications typically require more than 40,000 hours of reliable operation at a temperature of −35 °C to 40 °C (−31 °F to 104 °F), while automotive fuel cells require a 5,000-hour lifespan (the equivalent of 240,000 km (150,000 mi)) under extreme temperatures. Current service life is 2,500 hours (about 75,000 miles). Automotive engines must also be able to start reliably at −30 °C (−22 °F) and have a high power-to-volume ratio (typically 2.5 kW/L).
    Limited carbon monoxide tolerance of some (non-PEDOT) cathodes.

    Phosphoric acid fuel cell (PAFC)

    Phosphoric acid fuel cells (PAFC) were first designed and introduced in 1961 by G. V. Elmore and H. A. Tanner. In these cells phosphoric acid is used as a non-conductive electrolyte to pass positive hydrogen ions from the anode to the cathode. These cells commonly work in temperatures of 150 to 200 degrees Celsius. This high temperature will cause heat and energy loss if the heat is not removed and used properly. This heat can be used to produce steam for air conditioning systems or any other thermal energy consuming system. Using this heat in cogeneration can enhance the efficiency of phosphoric acid fuel cells from 40 to 50% to about 80%. Phosphoric acid, the electrolyte used in PAFCs, is a non-conductive liquid acid which forces electrons to travel from anode to cathode through an external electrical circuit. Since the hydrogen ion production rate on the anode is small, platinum is used as catalyst to increase this ionization rate. A key disadvantage of these cells is the use of an acidic electrolyte. This increases the corrosion or oxidation of components exposed to phosphoric acid.

    Solid acid fuel cell (SAFC)

    Solid acid fuel cells (SAFCs) are characterized by the use of a solid acid material as the electrolyte. At low temperatures, solid acids have an ordered molecular structure like most salts. At warmer temperatures (between 140 and 150 °C for CsHSO4), some solid acids undergo a phase transition to become highly disordered "superprotonic" structures, which increases conductivity by several orders of magnitude. The first proof-of-concept SAFCs were developed in 2000 using cesium hydrogen sulfate (CsHSO4). Current SAFC systems use cesium dihydrogen phosphate (CsH2PO4) and have demonstrated lifetimes in the thousands of hours.

    Alkaline fuel cell (AFC)

    The alkaline fuel cell or hydrogen-oxygen fuel cell was designed and first demonstrated publicly by Francis Thomas Bacon in 1959. It was used as a primary source of electrical energy in the Apollo space program. The cell consists of two porous carbon electrodes impregnated with a suitable catalyst such as Pt, Ag, CoO, etc. The space between the two electrodes is filled with a concentrated solution of KOH or NaOH which serves as an electrolyte. H2 gas and O2 gas are bubbled into the electrolyte through the porous carbon electrodes. Thus the overall reaction involves the combination of hydrogen gas and oxygen gas to form water. The cell runs continuously until the reactant's supply is exhausted. This type of cell operates efficiently in the temperature range 343–413 K and provides a potential of about 0.9 V. AAEMFC is a type of AFC which employs a solid polymer electrolyte instead of aqueous potassium hydroxide (KOH) and it is superior to aqueous AFC.

    High-temperature fuel cells

    Solid oxide fuel cell

    Solid oxide fuel cells (SOFCs) use a solid material, most commonly a ceramic material called yttria-stabilized zirconia (YSZ), as the electrolyte. Because SOFCs are made entirely of solid materials, they are not limited to the flat plane configuration of other types of fuel cells and are often designed as rolled tubes. They require high operating temperatures (800–1000 °C) and can be run on a variety of fuels including natural gas.

    SOFCs are unique since in those, negatively charged oxygen ions travel from the cathode (positive side of the fuel cell) to the anode (negative side of the fuel cell) instead of positively charged hydrogen ions travelling from the anode to the cathode, as is the case in all other types of fuel cells. Oxygen gas is fed through the cathode, where it absorbs electrons to create oxygen ions. The oxygen ions then travel through the electrolyte to react with hydrogen gas at the anode. The reaction at the anode produces electricity and water as by-products. Carbon dioxide may also be a by-product depending on the fuel, but the carbon emissions from an SOFC system are less than those from a fossil fuel combustion plant. The chemical reactions for the SOFC system can be expressed as follows:

    Anode reaction: 2H2 + 2O2− → 2H2O + 4e
    Cathode reaction: O2 + 4e → 2O2−
    Overall cell reaction: 2H2 + O2 → 2H2O

    SOFC systems can run on fuels other than pure hydrogen gas. However, since hydrogen is necessary for the reactions listed above, the fuel selected must contain hydrogen atoms. For the fuel cell to operate, the fuel must be converted into pure hydrogen gas. SOFCs are capable of internally reforming light hydrocarbons such as methane (natural gas), propane and butane. These fuel cells are at an early stage of development.

    Challenges exist in SOFC systems due to their high operating temperatures. One such challenge is the potential for carbon dust to build up on the anode, which slows down the internal reforming process. Research to address this "carbon coking" issue at the University of Pennsylvania has shown that the use of copper-based cermet (heat-resistant materials made of ceramic and metal) can reduce coking and the loss of performance. Another disadvantage of SOFC systems is slow start-up time, making SOFCs less useful for mobile applications. Despite these disadvantages, a high operating temperature provides an advantage by removing the need for a precious metal catalyst like platinum, thereby reducing cost. Additionally, waste heat from SOFC systems may be captured and reused, increasing the theoretical overall efficiency to as high as 80–85%.

    The high operating temperature is largely due to the physical properties of the YSZ electrolyte. As temperature decreases, so does the ionic conductivity of YSZ. Therefore, to obtain optimum performance of the fuel cell, a high operating temperature is required. According to their website, Ceres Power, a UK SOFC fuel cell manufacturer, has developed a method of reducing the operating temperature of their SOFC system to 500–600 degrees Celsius. They replaced the commonly used YSZ electrolyte with a CGO (cerium gadolinium oxide) electrolyte. The lower operating temperature allows them to use stainless steel instead of ceramic as the cell substrate, which reduces cost and start-up time of the system.

    Molten-carbonate fuel cell (MCFC)

    Molten carbonate fuel cells (MCFCs) require a high operating temperature, 650 °C (1,200 °F), similar to SOFCs. MCFCs use lithium potassium carbonate salt as an electrolyte, and this salt liquefies at high temperatures, allowing for the movement of charge within the cell – in this case, negative carbonate ions.

    Like SOFCs, MCFCs are capable of converting fossil fuel to a hydrogen-rich gas in the anode, eliminating the need to produce hydrogen externally. The reforming process creates CO2 emissions. MCFC-compatible fuels include natural gas, biogas and gas produced from coal. The hydrogen in the gas reacts with carbonate ions from the electrolyte to produce water, carbon dioxide, electrons and small amounts of other chemicals. The electrons travel through an external circuit creating electricity and return to the cathode. There, oxygen from the air and carbon dioxide recycled from the anode react with the electrons to form carbonate ions that replenish the electrolyte, completing the circuit. The chemical reactions for an MCFC system can be expressed as follows:

    Anode reaction: CO32− + H2 → H2O + CO2 + 2e
    Cathode reaction: CO2 + ½O2 + 2e → CO32−
    Overall cell reaction: H2 + ½O2 → H2O

    As with SOFCs, MCFC disadvantages include slow start-up times because of their high operating temperature. This makes MCFC systems not suitable for mobile applications, and this technology will most likely be used for stationary fuel cell purposes. The main challenge of MCFC technology is the cells' short life span. The high-temperature and carbonate electrolyte lead to corrosion of the anode and cathode. These factors accelerate the degradation of MCFC components, decreasing the durability and cell life. Researchers are addressing this problem by exploring corrosion-resistant materials for components as well as fuel cell designs that may increase cell life without decreasing performance.

    MCFCs hold several advantages over other fuel cell technologies, including their resistance to impurities. They are not prone to "carbon coking", which refers to carbon build-up on the anode that results in reduced performance by slowing down the internal fuel reforming process. Therefore, carbon-rich fuels like gases made from coal are compatible with the system. The United States Department of Energy claims that coal, itself, might even be a fuel option in the future, assuming the system can be made resistant to impurities such as sulfur and particulates that result from converting coal into hydrogen. MCFCs also have relatively high efficiencies. They can reach a fuel-to-electricity efficiency of 50%, considerably higher than the 37–42% efficiency of a phosphoric acid fuel cell plant. Efficiencies can be as high as 65% when the fuel cell is paired with a turbine, and 85% if heat is captured and used in a combined heat and power (CHP) system.

    FuelCell Energy, a Connecticut-based fuel cell manufacturer, develops and sells MCFC fuel cells. The company says that their MCFC products range from 300 kW to 2.8 MW systems that achieve 47% electrical efficiency and can utilize CHP technology to obtain higher overall efficiencies. One product, the DFC-ERG, is combined with a gas turbine and, according to the company, it achieves an electrical efficiency of 65%.

    Electric storage fuel cell

    The electric storage fuel cell is a conventional battery chargeable by electric power input, using the conventional electro-chemical effect. However, the battery further includes hydrogen (and oxygen) inputs for alternatively charging the battery chemically.

    Comparison of fuel cell types

    Anode
    The electrode at which oxidation (a loss of electrons) takes place. For fuel cells and other galvanic cells, the anode is the negative terminal; for electrolytic cells (where electrolysis occurs), the anode is the positive terminal.
    Aqueous solution
    Of, relating to, or resembling water
    Made from, with, or by water.
    Catalyst
    A chemical substance that increases the rate of a reaction without being consumed; after the reaction, it can potentially be recovered from the reaction mixture and is chemically unchanged. The catalyst lowers the activation energy required, allowing the reaction to proceed more quickly or at a lower temperature. In a fuel cell, the catalyst facilitates the reaction of oxygen and hydrogen. It is usually made of platinum powder very thinly coated onto carbon paper or cloth. The catalyst is rough and porous so the maximum surface area of the platinum can be exposed to the hydrogen or oxygen. The platinum-coated side of the catalyst faces the membrane in the fuel cell.
    Cathode
    The electrode at which reduction (a gain of electrons) occurs. For fuel cells and other galvanic cells, the cathode is the positive terminal; for electrolytic cells (where electrolysis occurs), the cathode is the negative terminal.
    Electrolyte
    A substance that conducts charged ions from one electrode to the other in a fuel cell, battery, or electrolyzer.
    Fuel cell stack
    Individual fuel cells connected in a series. Fuel cells are stacked to increase voltage.
    Matrix
    something within or from which something else originates, develops, or takes form.
    Membrane
    The separating layer in a fuel cell that acts as electrolyte (an ion-exchanger) as well as a barrier film separating the gases in the anode and cathode compartments of the fuel cell.
    Molten carbonate fuel cell (MCFC)
    A type of fuel cell that contains a molten carbonate electrolyte. Carbonate ions (CO32−) are transported from the cathode to the anode. Operating temperatures are typically near 650 °C.
    Phosphoric acid fuel cell (PAFC)
    A type of fuel cell in which the electrolyte consists of concentrated phosphoric acid (H3PO4). Protons (H+) are transported from the anode to the cathode. The operating temperature range is generally 160–220 °C.
    Proton-exchange membrane fuel cell (PEM)
    A fuel cell incorporating a solid polymer membrane used as its electrolyte. Protons (H+) are transported from the anode to the cathode. The operating temperature range is generally 60–100 °C for Low Temperature Proton-exchange membrane fuel cell (LT-PEMFC). PEM fuel cell with operating temperature of 120-200 °C is called High Temperature Proton-exchange membrane fuel cell (HT-PEMFC).
    Solid oxide fuel cell (SOFC)
    A type of fuel cell in which the electrolyte is a solid, nonporous metal oxide, typically zirconium oxide (ZrO2) treated with Y2O3, and O2− is transported from the cathode to the anode. Any CO in the reformate gas is oxidized to CO2 at the anode. Temperatures of operation are typically 800–1,000 °C.
    Solution
    An act or the process by which a solid, liquid, or gaseous substance is homogeneously mixed with a liquid or sometimes a gas or solid.
    A homogeneous mixture formed by this process; especially : a single-phase liquid system.
    The condition of being dissolved.

    Efficiency of leading fuel cell types

    Theoretical maximum efficiency

    The energy efficiency of a system or device that converts energy is measured by the ratio of the amount of useful energy put out by the system ("output energy") to the total amount of energy that is put in ("input energy") or by useful output energy as a percentage of the total input energy. In the case of fuel cells, useful output energy is measured in electrical energy produced by the system. Input energy is the energy stored in the fuel. According to the U.S. Department of Energy, fuel cells are generally between 40 and 60% energy efficient. This is higher than some other systems for energy generation. For example, the typical internal combustion engine of a car is about 25% energy efficient. In combined heat and power (CHP) systems, the heat produced by the fuel cell is captured and put to use, increasing the efficiency of the system to up to 85–90%.

    The theoretical maximum efficiency of any type of power generation system is never reached in practice, and it does not consider other steps in power generation, such as production, transportation and storage of fuel and conversion of the electricity into mechanical power. However, this calculation allows the comparison of different types of power generation. The theoretical maximum efficiency of a fuel cell approaches 100%, while the theoretical maximum efficiency of internal combustion engines is approximately 58%.

    In practice

    In a fuel cell vehicle the tank-to-wheel efficiency is greater than 45% at low loads and shows average values of about 36% when a driving cycle like the NEDC (New European Driving Cycle) is used as test procedure. The comparable NEDC value for a Diesel vehicle is 22%. In 2008 Honda released a demonstration fuel cell electric vehicle (the Honda FCX Clarity) with fuel stack claiming a 60% tank-to-wheel efficiency.

    It is also important to take losses due to fuel production, transportation, and storage into account. Fuel cell vehicles running on compressed hydrogen may have a power-plant-to-wheel efficiency of 22% if the hydrogen is stored as high-pressure gas, and 17% if it is stored as liquid hydrogen.[70] Fuel cells cannot store energy like a battery, except as hydrogen, but in some applications, such as stand-alone power plants based on discontinuous sources such as solar or wind power, they are combined with electrolyzers and storage systems to form an energy storage system. As of 2019, 90% of hydrogen was used for oil refining, chemicals and fertilizer production, and 98% of hydrogen is produced by steam methane reforming, which emits carbon dioxide. The overall efficiency (electricity to hydrogen and back to electricity) of such plants (known as round-trip efficiency), using pure hydrogen and pure oxygen can be "from 35 up to 50 percent", depending on gas density and other conditions. The electrolyzer/fuel cell system can store indefinite quantities of hydrogen, and is therefore suited for long-term storage.

    Solid-oxide fuel cells produce heat from the recombination of the oxygen and hydrogen. The ceramic can run as hot as 800 degrees Celsius. This heat can be captured and used to heat water in a micro combined heat and power (m-CHP) application. When the heat is captured, total efficiency can reach 80–90% at the unit, but does not consider production and distribution losses. CHP units are being developed today for the European home market.

    Professor Jeremy P. Meyers, in the Electrochemical Society journal Interface in 2008, wrote, "While fuel cells are efficient relative to combustion engines, they are not as efficient as batteries, primarily due to the inefficiency of the oxygen reduction reaction (and ... the oxygen evolution reaction, should the hydrogen be formed by electrolysis of water).... [T]hey make the most sense for operation disconnected from the grid, or when fuel can be provided continuously. For applications that require frequent and relatively rapid start-ups ... where zero emissions are a requirement, as in enclosed spaces such as warehouses, and where hydrogen is considered an acceptable reactant, a [PEM fuel cell] is becoming an increasingly attractive choice [if exchanging batteries is inconvenient]". In 2013 military organizations were evaluating fuel cells to determine if they could significantly reduce the battery weight carried by soldiers.

    Applications

    Type 212 submarine with fuel cell propulsion of the German Navy in dry dock

    Power

    Stationary fuel cells are used for commercial, industrial and residential primary and backup power generation. Fuel cells are very useful as power sources in remote locations, such as spacecraft, remote weather stations, large parks, communications centers, rural locations including research stations, and in certain military applications. A fuel cell system running on hydrogen can be compact and lightweight, and have no major moving parts. Because fuel cells have no moving parts and do not involve combustion, in ideal conditions they can achieve up to 99.9999% reliability. This equates to less than one minute of downtime in a six-year period.

    Since fuel cell electrolyzer systems do not store fuel in themselves, but rather rely on external storage units, they can be successfully applied in large-scale energy storage, rural areas being one example. There are many different types of stationary fuel cells so efficiencies vary, but most are between 40% and 60% energy efficient. However, when the fuel cell's waste heat is used to heat a building in a cogeneration system this efficiency can increase to 85%. This is significantly more efficient than traditional coal power plants, which are only about one third energy efficient. Assuming production at scale, fuel cells could save 20–40% on energy costs when used in cogeneration systems. Fuel cells are also much cleaner than traditional power generation; a fuel cell power plant using natural gas as a hydrogen source would create less than one ounce of pollution (other than CO2) for every 1,000 kW·h produced, compared to 25 pounds of pollutants generated by conventional combustion systems. Fuel Cells also produce 97% less nitrogen oxide emissions than conventional coal-fired power plants.

    One such pilot program is operating on Stuart Island in Washington State. There the Stuart Island Energy Initiative has built a complete, closed-loop system: Solar panels power an electrolyzer, which makes hydrogen. The hydrogen is stored in a 500-U.S.-gallon (1,900 L) tank at 200 pounds per square inch (1,400 kPa), and runs a ReliOn fuel cell to provide full electric back-up to the off-the-grid residence. Another closed system loop was unveiled in late 2011 in Hempstead, NY.

    Fuel cells can be used with low-quality gas from landfills or waste-water treatment plants to generate power and lower methane emissions. A 2.8 MW fuel cell plant in California is said to be the largest of the type. Small-scale (sub-5kWhr) fuel cells are being developed for use in residential off-grid deployment.

    Cogeneration

    Combined heat and power (CHP) fuel cell systems, including micro combined heat and power (MicroCHP) systems are used to generate both electricity and heat for homes (see home fuel cell), office building and factories. The system generates constant electric power (selling excess power back to the grid when it is not consumed), and at the same time produces hot air and water from the waste heat. As the result CHP systems have the potential to save primary energy as they can make use of waste heat which is generally rejected by thermal energy conversion systems. A typical capacity range of home fuel cell is 1–3 kWel, 4–8 kWth. CHP systems linked to absorption chillers use their waste heat for refrigeration.

    The waste heat from fuel cells can be diverted during the summer directly into the ground providing further cooling while the waste heat during winter can be pumped directly into the building. The University of Minnesota owns the patent rights to this type of system.

    Co-generation systems can reach 85% efficiency (40–60% electric and the remainder as thermal). Phosphoric-acid fuel cells (PAFC) comprise the largest segment of existing CHP products worldwide and can provide combined efficiencies close to 90%. Molten carbonate (MCFC) and solid-oxide fuel cells (SOFC) are also used for combined heat and power generation and have electrical energy efficiencies around 60%. Disadvantages of co-generation systems include slow ramping up and down rates, high cost and short lifetime. Also their need to have a hot water storage tank to smooth out the thermal heat production was a serious disadvantage in the domestic market place where space in domestic properties is at a great premium.

    Delta-ee consultants stated in 2013 that with 64% of global sales the fuel cell micro-combined heat and power passed the conventional systems in sales in 2012. The Japanese ENE FARM project will pass 100,000 FC mCHP systems in 2014, 34.213 PEMFC and 2.224 SOFC were installed in the period 2012–2014, 30,000 units on LNG and 6,000 on LPG.

    Fuel cell electric vehicles (FCEVs)

    Configuration of components in a fuel cell car
     
    Element One fuel cell vehicle

    Automobiles

    By year-end 2019, about 18,000 FCEVs had been leased or sold worldwide. Three fuel cell electric vehicles have been introduced for commercial lease and sale: the Honda Clarity, Toyota Mirai and the Hyundai ix35 FCEV. Additional demonstration models include the Honda FCX Clarity, and Mercedes-Benz F-Cell. As of June 2011 demonstration FCEVs had driven more than 4,800,000 km (3,000,000 mi), with more than 27,000 refuelings. Fuel cell electric vehicles feature an average range of 314 miles between refuelings. They can be refueled in less than 5 minutes. The U.S. Department of Energy's Fuel Cell Technology Program states that, as of 2011, fuel cells achieved 53–59% efficiency at one-quarter power and 42–53% vehicle efficiency at full power, and a durability of over 120,000 km (75,000 mi) with less than 10% degradation. In a 2017 Well-to-Wheels simulation analysis that "did not address the economics and market constraints", General Motors and its partners estimated that per mile traveled, a fuel cell electric vehicle running on compressed gaseous hydrogen produced from natural gas could use about 40% less energy and emit 45% less greenhouse gasses than an internal combustion vehicle.

    In 2015, Toyota introduced its first fuel cell vehicle, the Mirai, at a price of $57,000. Hyundai introduced the limited production Hyundai ix35 FCEV under a lease agreement. In 2016, Honda started leasing the Honda Clarity Fuel Cell. In 2020, Toyota introduced the second generation of its Mirai brand, improving fuel efficiency and expanding range compared to the original Sedan 2014 model.

    Criticism

    Some commentators believe that hydrogen fuel cell cars will never become economically competitive with other technologies or that it will take decades for them to become profitable. Elon Musk, CEO of battery-electric vehicle maker Tesla Motors, stated in 2015 that fuel cells for use in cars will never be commercially viable because of the inefficiency of producing, transporting and storing hydrogen and the flammability of the gas, among other reasons.

    In 2012, Lux Research, Inc. issued a report that stated: "The dream of a hydrogen economy ... is no nearer". It concluded that "Capital cost ... will limit adoption to a mere 5.9 GW" by 2030, providing "a nearly insurmountable barrier to adoption, except in niche applications". The analysis concluded that, by 2030, PEM stationary market will reach $1 billion, while the vehicle market, including forklifts, will reach a total of $2 billion. Other analyses cite the lack of an extensive hydrogen infrastructure in the U.S. as an ongoing challenge to Fuel Cell Electric Vehicle commercialization.

    In 2014, Joseph Romm, the author of The Hype About Hydrogen (2005), said that FCVs still had not overcome the high fueling cost, lack of fuel-delivery infrastructure, and pollution caused by producing hydrogen. "It would take several miracles to overcome all of those problems simultaneously in the coming decades." He concluded that renewable energy cannot economically be used to make hydrogen for an FCV fleet "either now or in the future." Greentech Media's analyst reached similar conclusions in 2014. In 2015, Clean Technica listed some of the disadvantages of hydrogen fuel cell vehicles. So did Car Throttle.

    A 2019 video by Real Engineering noted that, notwithstanding the introduction of vehicles that run on hydrogen, using hydrogen as a fuel for cars does not help to reduce carbon emissions from transportation. The 95% of hydrogen still produced from fossil fuels releases carbon dioxide, and producing hydrogen from water is an energy-consuming process. Storing hydrogen requires more energy either to cool it down to the liquid state or to put it into tanks under high pressure, and delivering the hydrogen to fueling stations requires more energy and may release more carbon. The hydrogen needed to move a FCV a kilometer costs approximately 8 times as much as the electricity needed to move a BEV the same distance. A 2020 assessment concluded that hydrogen vehicles are still only 38% efficient, while battery EVs are 80% efficient.

    Buses

    As of August 2011, there were about 100 fuel cell buses in service around the world. Most of these were manufactured by UTC Power, Toyota, Ballard, Hydrogenics, and Proton Motor. UTC buses had driven more than 970,000 km (600,000 mi) by 2011. Fuel cell buses have from 39% to 141% higher fuel economy than diesel buses and natural gas buses.

    As of 2019, the NREL was evaluating several current and planned fuel cell bus projects in the U.S.

    Trucks

    In December 2020, Toyota and Hino Motors, together with Seven-Eleven (Japan), FamilyMart and Lawson announced that they have agreed to jointly consider introducing light-duty fuel cell electric trucks (light-duty FCETs). Lawson started testing for low temperature delivery at the end of July 2021 in Tokyo, using a Hino Dutro in which the Toyota Mirai fuel cell is implemented. FamilyMart started testing in Okazaki city.

    In August 2021, Toyota announced their plan to make fuel cell modules at its Kentucky auto-assembly plant for use in zero-emission big rigs and heavy-duty commercial vehicles. They plan to begin assembling the electrochemical devices in 2023.

    Forklifts

    A fuel cell forklift (also called a fuel cell lift truck) is a fuel cell-powered industrial forklift truck used to lift and transport materials. In 2013 there were over 4,000 fuel cell forklifts used in material handling in the US, of which 500 received funding from DOE (2012). Fuel cell fleets are operated by various companies, including Sysco Foods, FedEx Freight, GENCO (at Wegmans, Coca-Cola, Kimberly Clark, and Whole Foods), and H-E-B Grocers. Europe demonstrated 30 fuel cell forklifts with Hylift and extended it with HyLIFT-EUROPE to 200 units, with other projects in France and Austria. Pike Research projected in 2011 that fuel cell-powered forklifts would be the largest driver of hydrogen fuel demand by 2020.

    Most companies in Europe and the US do not use petroleum-powered forklifts, as these vehicles work indoors where emissions must be controlled and instead use electric forklifts. Fuel cell-powered forklifts can provide benefits over battery-powered forklifts as they can be refueled in 3 minutes and they can be used in refrigerated warehouses, where their performance is not degraded by lower temperatures. The FC units are often designed as drop-in replacements.

    Motorcycles and bicycles

    In 2005, a British manufacturer of hydrogen-powered fuel cells, Intelligent Energy (IE), produced the first working hydrogen-run motorcycle called the ENV (Emission Neutral Vehicle). The motorcycle holds enough fuel to run for four hours, and to travel 160 km (100 mi) in an urban area, at a top speed of 80 km/h (50 mph). In 2004 Honda developed a fuel cell motorcycle that utilized the Honda FC Stack.

    Other examples of motorbikes and bicycles that use hydrogen fuel cells include the Taiwanese company APFCT's scooter using the fueling system from Italy's Acta SpA and the Suzuki Burgman scooter with an IE fuel cell that received EU Whole Vehicle Type Approval in 2011. Suzuki Motor Corp. and IE have announced a joint venture to accelerate the commercialization of zero-emission vehicles.

    Airplanes

    In 2003, the world's first propeller-driven airplane to be powered entirely by a fuel cell was flown. The fuel cell was a stack design that allowed the fuel cell to be integrated with the plane's aerodynamic surfaces. Fuel cell-powered unmanned aerial vehicles (UAV) include a Horizon fuel cell UAV that set the record distance flown for a small UAV in 2007. Boeing researchers and industry partners throughout Europe conducted experimental flight tests in February 2008 of a manned airplane powered only by a fuel cell and lightweight batteries. The fuel cell demonstrator airplane, as it was called, used a proton-exchange membrane (PEM) fuel cell/lithium-ion battery hybrid system to power an electric motor, which was coupled to a conventional propeller.

    In 2009, the Naval Research Laboratory's (NRL's) Ion Tiger utilized a hydrogen-powered fuel cell and flew for 23 hours and 17 minutes. Fuel cells are also being tested and considered to provide auxiliary power in aircraft, replacing fossil fuel generators that were previously used to start the engines and power on board electrical needs, while reducing carbon emissions. In 2016 a Raptor E1 drone made a successful test flight using a fuel cell that was lighter than the lithium-ion battery it replaced. The flight lasted 10 minutes at an altitude of 80 metres (260 ft), although the fuel cell reportedly had enough fuel to fly for two hours. The fuel was contained in approximately 100 solid 1 square centimetre (0.16 sq in) pellets composed of a proprietary chemical within an unpressurized cartridge. The pellets are physically robust and operate at temperatures as warm as 50 °C (122 °F). The cell was from Arcola Energy.

    Lockheed Martin Skunk Works Stalker is an electric UAV powered by solid oxide fuel cell.

    Boats

    The world's first certified fuel cell boat (HYDRA), in Leipzig/Germany

    The world's first fuel cell boat HYDRA used an AFC system with 6.5 kW net output. Amsterdam introduced fuel cell-powered boats that ferry people around the city's canals.

    Submarines

    The Type 212 submarines of the German and Italian navies use fuel cells to remain submerged for weeks without the need to surface.

    The U212A is a non-nuclear submarine developed by German naval shipyard Howaldtswerke Deutsche Werft. The system consists of nine PEM fuel cells, providing between 30 kW and 50 kW each. The ship is silent, giving it an advantage in the detection of other submarines. A naval paper has theorized about the possibility of a nuclear-fuel cell hybrid whereby the fuel cell is used when silent operations are required and then replenished from the Nuclear reactor (and water).

    Portable power systems

    Portable fuel cell systems are generally classified as weighing under 10 kg and providing power of less than 5 kW. The potential market size for smaller fuel cells is quite large with an up to 40% per annum potential growth rate and a market size of around $10 billion, leading a great deal of research to be devoted to the development of portable power cells. Within this market two groups have been identified. The first is the microfuel cell market, in the 1-50 W range for power smaller electronic devices. The second is the 1-5 kW range of generators for larger scale power generation (e.g. military outposts, remote oil fields).

    Microfuel cells are primarily aimed at penetrating the market for phones and laptops. This can be primarily attributed to the advantageous energy density provided by fuel cells over a lithium-ion battery, for the entire system. For a battery, this system includes the charger as well as the battery itself. For the fuel cell this system would include the cell, the necessary fuel and peripheral attachments. Taking the full system into consideration, fuel cells have been shown to provide 530Wh/kg compared to 44 Wh/kg for lithium ion batteries. However, while the weight of fuel cell systems offer a distinct advantage the current costs are not in their favor. while a battery system will generally cost around $1.20 per Wh, fuel cell systems cost around $5 per Wh, putting them at a significant disadvantage.

    As power demands for cell phones increase, fuel cells could become much more attractive options for larger power generation. The demand for longer on time on phones and computers is something often demanded by consumers so fuel cells could start to make strides into laptop and cell phone markets. The price will continue to go down as developments in fuel cells continues to accelerate. Current strategies for improving micro fuel cells is through the use of carbon nanotubes. It was shown by Girishkumar et al. that depositing nanotubes on electrode surfaces allows for substantially greater surface area increasing the oxygen reduction rate.

    Fuel cells for use in larger scale operations also show much promise. Portable power systems that use fuel cells can be used in the leisure sector (i.e. RVs, cabins, marine), the industrial sector (i.e. power for remote locations including gas/oil wellsites, communication towers, security, weather stations), and in the military sector. SFC Energy is a German manufacturer of direct methanol fuel cells for a variety of portable power systems. Ensol Systems Inc. is an integrator of portable power systems, using the SFC Energy DMFC. The key advantage of fuel cells in this market is the great power generation per weight. While fuel cells can be expensive, for remote locations that require dependable energy fuel cells hold great power. For a 72-h excursion the comparison in weight is substantial, with a fuel cell only weighing 15 pounds compared to 29 pounds of batteries needed for the same energy.

    Other applications

    • Providing power for base stations or cell sites
    • Distributed generation
    • Emergency power systems are a type of fuel cell system, which may include lighting, generators and other apparatus, to provide backup resources in a crisis or when regular systems fail. They find uses in a wide variety of settings from residential homes to hospitals, scientific laboratories, data centers.
    • Telecommunication equipment and modern naval ships.
    • An uninterrupted power supply (UPS) provides emergency power and, depending on the topology, provide line regulation as well to connected equipment by supplying power from a separate source when utility power is not available. Unlike a standby generator, it can provide instant protection from a momentary power interruption.
    • Base load power plants
    • Solar Hydrogen Fuel Cell Water Heating
    • Hybrid vehicles, pairing the fuel cell with either an ICE or a battery.
    • Notebook computers for applications where AC charging may not be readily available.
    • Portable charging docks for small electronics (e.g. a belt clip that charges a cell phone or PDA).
    • Smartphones, laptops and tablets.
    • Small heating appliances
    • Food preservation, achieved by exhausting the oxygen and automatically maintaining oxygen exhaustion in a shipping container, containing, for example, fresh fish.
    • Breathalyzers, where the amount of voltage generated by a fuel cell is used to determine the concentration of fuel (alcohol) in the sample.
    • Carbon monoxide detector, electrochemical sensor.

    Fueling stations

    According to FuelCellsWorks, an industry group, at the end of 2019, 330 hydrogen refueling stations were open to the public worldwide. As of June 2020, there were 178 publicly available hydrogen stations in operation in Asia. 114 of these were in Japan. There were at least 177 stations in Europe, and about half of these were in Germany. There were 44 publicly accessible stations in the US, 42 of which were located in California.

    A hydrogen fueling station costs between $1 million and $4 million to build.

    Markets and economics

    In 2012, fuel cell industry revenues exceeded $1 billion market value worldwide, with Asian pacific countries shipping more than 3/4 of the fuel cell systems worldwide. However, as of January 2014, no public company in the industry had yet become profitable. There were 140,000 fuel cell stacks shipped globally in 2010, up from 11,000 shipments in 2007, and from 2011 to 2012 worldwide fuel cell shipments had an annual growth rate of 85%. Tanaka Kikinzoku expanded its manufacturing facilities in 2011. Approximately 50% of fuel cell shipments in 2010 were stationary fuel cells, up from about a third in 2009, and the four dominant producers in the Fuel Cell Industry were the United States, Germany, Japan and South Korea. The Department of Energy Solid State Energy Conversion Alliance found that, as of January 2011, stationary fuel cells generated power at approximately $724 to $775 per kilowatt installed. In 2011, Bloom Energy, a major fuel cell supplier, said that its fuel cells generated power at 9–11 cents per kilowatt-hour, including the price of fuel, maintenance, and hardware.

    Industry groups predict that there are sufficient platinum resources for future demand, and in 2007, research at Brookhaven National Laboratory suggested that platinum could be replaced by a gold-palladium coating, which may be less susceptible to poisoning and thereby improve fuel cell lifetime. Another method would use iron and sulphur instead of platinum. This would lower the cost of a fuel cell (as the platinum in a regular fuel cell costs around US$1,500, and the same amount of iron costs only around US$1.50). The concept was being developed by a coalition of the John Innes Centre and the University of Milan-Bicocca. PEDOT cathodes are immune to monoxide poisoning.

    In 2016, Samsung "decided to drop fuel cell-related business projects, as the outlook of the market isn't good".

    Research and development

  • 2005: Georgia Institute of Technology researchers used triazole to raise the operating temperature of PEM fuel cells from below 100 °C to over 125 °C, claiming this will require less carbon-monoxide purification of the hydrogen fuel.
  • 2008: Monash University, Melbourne used PEDOT as a cathode.
  • 2009: Researchers at the University of Dayton, in Ohio, showed that arrays of vertically grown carbon nanotubes could be used as the catalyst in fuel cells. The same year, a nickel bisdiphosphine-based catalyst for fuel cells was demonstrated.
  • 2013: British firm ACAL Energy developed a fuel cell that it said can run for 10,000 hours in simulated driving conditions. It asserted that the cost of fuel cell construction can be reduced to $40/kW (roughly $9,000 for 300 HP).
  • 2014: Researchers in Imperial College London developed a new method for regeneration of hydrogen sulfide contaminated PEFCs. They recovered 95–100% of the original performance of a hydrogen sulfide contaminated PEFC. They were successful in rejuvenating a SO2 contaminated PEFC too. This regeneration method is applicable to multiple cell stacks.

The Hype About Hydrogen

From Wikipedia, the free encyclopedia
 
The Hype About Hydrogen
HypeCover.jpg
AuthorJoseph J. Romm
LanguageEnglish
PublisherIsland Press
Publication date
2004
ISBN1-55963-703-X
OCLC53138756
333.79/68 22
LC ClassTP261.H9 .R65 2004
Preceded byCool Companies (1999) 
Followed byHell and High Water 
Cover of German version

The Hype About Hydrogen: Fact and Fiction in the Race to Save the Climate is a book by Joseph J. Romm, published in 2004 by Island Press and updated in 2005. The book has been translated into German as Der Wasserstoff-Boom. Romm is an expert on clean energy, advanced vehicles, energy security, and greenhouse gas mitigation.

Over 200 publications, including Scientific American, Forbes magazine and The New York Times, have cited this book. The book was named one of the best science and technology books of 2004 by Library Journal.

The thrust of the book is that hydrogen is not economically feasible to use for transportation, nor will its use reduce global warming, because of the greenhouse gases generated during production and transportation of hydrogen, the low energy content per volume and weight of the container, the cost of the fuel cells, and the cost of the infrastructure for refueling. The author argues that a major effort to introduce hydrogen cars before 2030 would actually undermine efforts to reduce emissions of heat-trapping greenhouse gases such as carbon dioxide.

Description of the book

The Hype about Hydrogen contends that global warming and U.S. reliance on foreign fuel imports cannot be solved by the hypothetical hydrogen economy that has been advanced as a possible solution to these problems, and that "neither government policy nor business investment should be based on the belief that hydrogen cars will have meaningful commercial success in the near or medium term."

The book explains how fuel cells work and compares different types. It then reviews the difficulties in marketing fuel cells for applications other than transportation and argues that these are in fact easier and more likely to happen sooner than transportation applications.

The history of hydrogen and its methods of production are then described. The book claims that the most common and cost-effective method of hydrogen production is from natural gas, which emits large amounts of CO2 (a greenhouse gas), since it would require too much electric power to produce hydrogen using the electrolysis method. The monetary costs of hydrogen fueling infrastructure for the U.S. are then estimated at half a trillion U.S. dollars, and the book describes additional energy and environment costs to liquefy and compress hydrogen for use in fueling stations.

The book goes on to discuss the hypothetical evolution of the cost of vehicles with fuel cells and with hydrogen-powered internal combustion engines, as well as possible adoption strategies. It then reviews the issue of the greenhouse effect and offers four reasons why hydrogen would not be useful in reducing greenhouse gas emissions:

  • Internal combustion engines continue to improve in efficiency.
  • Since hydrogen is likely to be made from combustion of fossil fuels, it produces CO2 and other greenhouse gases as part of the fuel cycle.
  • Fuel cells are likely to be much more expensive than competing technologies.
  • Fuels used to make hydrogen could achieve larger reductions in greenhouse gas emissions if used to replace the least efficient of the electric power plants.

The book then describes pilot projects in Iceland and California.

In its conclusion, the book states that hydrogen will not be widely available as a transportation fuel for a long time, and describes other strategies, including energy conservation techniques, to combat global warming.

Critical reception

The Hype about Hydrogen was named one of the best science and technology books of 2004 by Library Journal. The New York Review of Books stated that the book gives "the most direct answers" to the question on the promise of a near-term hydrogen economy, calling Romm "a hydrogen realist". The environmental community newsletter TerraGreen agrees with Romm in the claim that "the car of the near future is the hybrid vehicle", and cites the book's good reception by Toyota's advanced technologies group. The San Diego Union Tribune's 2004 review noted that Romm's "clear logic" reaches conclusions similar to an authoritative study issued by the National Academy of Sciences.

Three UC Davis scientists who also reviewed the book agreed on its basic premises, but claimed that Romm had made selective use of sources, for example, citing the highest cost estimates, adopting extremely high estimates of efficiency for advanced gasoline vehicles, and giving weight to controversial non-peer-reviewed studies. 

Romm and Prof. Andrew A. Frank co-authored an article, "Hybrid Vehicles Gain Traction", published in the April 2006 issue of Scientific American, in which they argue that hybrid cars that can be plugged into the electric grid (Plug-in hybrid electric vehicles), rather than hydrogen fuel cell vehicles, will soon become standard in the automobile industry.

 

Distillation

From Wikipedia, the free encyclopedia
https://en.wikipedia.org/wiki/Distillation

Laboratory display of distillation: 1: A heat source 2: Round bottomed flask 3: Still head 4: Thermometer/Boiling point temperature 5: Condenser 6: Cooling water in 7: Cooling water out 8: Distillate/receiving flask 9: Vacuum/gas inlet 10: Still receiver 11: Heat control 12: Stirrer speed control 13: Stirrer/heat plate 14: Heating (Oil/sand) bath 15: Stirring mechanism (not shown) e.g. boiling chips or mechanical stirrer 16: Cooling bath.

Distillation, or classical distillation, is the process of separating the components or substances from a liquid mixture by using selective boiling and condensation. Dry distillation is the heating of solid materials to produce gaseous products (which may condense into liquids or solids). Dry distillation may involve chemical changes such as destructive distillation or cracking and is not discussed under this article. Distillation may result in essentially complete separation (nearly pure components), or it may be a partial separation that increases the concentration of selected components in the mixture. In either case, the process exploits differences in the relative volatility of the mixture's components. In industrial applications, distillation is a unit operation of practically universal importance, but it is a physical separation process, not a chemical reaction.

Distillation has many applications. For example:

An installation used for distillation, especially of distilled beverages, is a distillery. The distillation equipment itself is a still.

History

Distillation equipment used by the 3rd century alchemist Zosimos of Panopolis, from the Byzantine Greek manuscript Parisinus graces.

Early evidence of distillation was found on Akkadian tablets dated c. 1200 BCE describing perfumery operations. The tablets provided textual evidence that an early primitive form of distillation was known to the Babylonians of ancient Mesopotamia. Early evidence of distillation was also found related to alchemists working in Alexandria in Roman Egypt in the 1st century CE.

Distillation was practiced in the ancient Indian subcontinent, which is evident from baked clay retorts and receivers found at Taxila, Shaikhan Dheri, and Charsadda in modern Pakistan, dating to the early centuries of the Common Era. These "Gandhara stills" were only capable of producing very weak liquor, as there was no efficient means of collecting the vapors at low heat. Distilled water has been in use since at least c. 200 CE, when Alexander of Aphrodisias described the process. Work on distilling other liquids continued in early Byzantine Egypt under Zosimus of Panopolis in the 3rd century.

Distillation in China may have begun during the Eastern Han dynasty (1st–2nd centuries CE), but the distillation of beverages began in the Jin (12th–13th centuries) and Southern Song (10th–13th centuries) dynasties, according to archaeological evidence.

Medieval Muslim chemists such as Jābir ibn Ḥayyān (Latin: Geber, ninth century) and Abū Bakr al-Rāzī (Latin: Rhazes, c. 865–925) experimented extensively with the distillation of various substances. The distillation of wine is attested in Arabic works attributed to al-Kindī (c. 801–873 CE) and to al-Fārābī (c. 872–950), and in the 28th book of al-Zahrāwī's (Latin: Abulcasis, 936–1013) Kitāb al-Taṣrīf (later translated into Latin as Liber servatoris). In the twelfth century, recipes for the production of aqua ardens ("burning water", i.e., ethanol) by distilling wine with salt started to appear in a number of Latin works, and by the end of the thirteenth century it had become a widely known substance among Western European chemists. Fractional distillation was developed by Tadeo Alderotti in the 13th century.

A still was found in an archaeological site in Qinglong, Hebei province, in China, dating back to the 12th century. Distilled beverages were common during the Yuan dynasty (13th–14th centuries).

In 1500, German alchemist Hieronymus Braunschweig published Liber de arte destillandi (The Book of the Art of Distillation), the first book solely dedicated to the subject of distillation, followed in 1512 by a much expanded version. In 1651, John French published The Art of Distillation, the first major English compendium on the practice, but it has been claimed that much of it derives from Braunschweig's work. This includes diagrams with people in them showing the industrial rather than bench scale of the operation.

Hieronymus Brunschwig's Liber de arte Distillandi de Compositis (Strassburg, 1512) Science History Institute
 
 
Distillation
 
Old Ukrainian vodka still
 
Simple liqueur distillation in East Timor

As alchemy evolved into the science of chemistry, vessels called retorts became used for distillations. Both alembics and retorts are forms of glassware with long necks pointing to the side at a downward angle to act as air-cooled condensers to condense the distillate and let it drip downward for collection. Later, copper alembics were invented. Riveted joints were often kept tight by using various mixtures, for instance a dough made of rye flour. These alembics often featured a cooling system around the beak, using cold water, for instance, which made the condensation of alcohol more efficient. These were called pot stills. Today, the retorts and pot stills have been largely supplanted by more efficient distillation methods in most industrial processes. However, the pot still is still widely used for the elaboration of some fine alcohols, such as cognac, Scotch whisky, Irish whiskey, tequila, rum, and some vodkas. Pot stills made of various materials (wood, clay, stainless steel) are also used by bootleggers in various countries. Small pot stills are also sold for use in the domestic production of flower water or essential oils.

Early forms of distillation involved batch processes using one vaporization and one condensation. Purity was improved by further distillation of the condensate. Greater volumes were processed by simply repeating the distillation. Chemists reportedly carried out as many as 500 to 600 distillations in order to obtain a pure compound.

In the early 19th century, the basics of modern techniques, including pre-heating and reflux, were developed. In 1822, Anthony Perrier developed one of the first continuous stills, and then, in 1826, Robert Stein improved that design to make his patent still. In 1830, Aeneas Coffey got a patent for improving the design even further. Coffey's continuous still may be regarded as the archetype of modern petrochemical units. The French engineer Armand Savalle developed his steam regulator around 1846. In 1877, Ernest Solvay was granted a U.S. Patent for a tray column for ammonia distillation, and the same and subsequent years saw developments in this theme for oils and spirits.

With the emergence of chemical engineering as a discipline at the end of the 19th century, scientific rather than empirical methods could be applied. The developing petroleum industry in the early 20th century provided the impetus for the development of accurate design methods, such as the McCabe–Thiele method by Ernest Thiele and the Fenske equation. The first industrial plant in the United States to use distillation as a means of ocean desalination opened in Freeport, Texas in 1961 with the hope of bringing water security to the region. The availability of powerful computers has allowed direct computer simulations of distillation columns.

Applications

The application of distillation can roughly be divided into four groups: laboratory scale, industrial distillation, distillation of herbs for perfumery and medicinals (herbal distillate), and food processing. The latter two are distinctively different from the former two in that distillation is not used as a true purification method but more to transfer all volatiles from the source materials to the distillate in the processing of beverages and herbs.

The main difference between laboratory scale distillation and industrial distillation are that laboratory scale distillation is often performed on a batch basis, whereas industrial distillation often occurs continuously. In batch distillation, the composition of the source material, the vapors of the distilling compounds, and the distillate change during the distillation. In batch distillation, a still is charged (supplied) with a batch of feed mixture, which is then separated into its component fractions, which are collected sequentially from most volatile to less volatile, with the bottoms – remaining least or non-volatile fraction – removed at the end. The still can then be recharged and the process repeated.

In continuous distillation, the source materials, vapors, and distillate are kept at a constant composition by carefully replenishing the source material and removing fractions from both vapor and liquid in the system. This results in a more detailed control of the separation process.

Idealized model

The boiling point of a liquid is the temperature at which the vapor pressure of the liquid equals the pressure around the liquid, enabling bubbles to form without being crushed. A special case is the normal boiling point, where the vapor pressure of the liquid equals the ambient atmospheric pressure.

It is a misconception that in a liquid mixture at a given pressure, each component boils at the boiling point corresponding to the given pressure, allowing the vapors of each component to collect separately and purely. However, this does not occur, even in an idealized system. Idealized models of distillation are essentially governed by Raoult's law and Dalton's law and assume that vapor–liquid equilibria are attained.

Raoult's law states that the vapor pressure of a solution is dependent on 1) the vapor pressure of each chemical component in the solution and 2) the fraction of solution each component makes up, a.k.a. the mole fraction. This law applies to ideal solutions, or solutions that have different components but whose molecular interactions are the same as or very similar to pure solutions.

Dalton's law states that the total pressure is the sum of the partial pressures of each individual component in the mixture. When a multi-component liquid is heated, the vapor pressure of each component will rise, thus causing the total vapor pressure to rise. When the total vapor pressure reaches the pressure surrounding the liquid, boiling occurs and liquid turns to gas throughout the bulk of the liquid. A mixture with a given composition has one boiling point at a given pressure when the components are mutually soluble. A mixture of constant composition does not have multiple boiling points.

An implication of one boiling point is that lighter components never cleanly "boil first". At boiling point, all volatile components boil, but for a component, its percentage in the vapor is the same as its percentage of the total vapor pressure. Lighter components have a higher partial pressure and, thus, are concentrated in the vapor, but heavier volatile components also have a (smaller) partial pressure and necessarily vaporize also, albeit at a lower concentration in the vapor. Indeed, batch distillation and fractionation succeed by varying the composition of the mixture. In batch distillation, the batch vaporizes, which changes its composition; in fractionation, liquid higher in the fractionation column contains more lights and boils at lower temperatures. Therefore, starting from a given mixture, it appears to have a boiling range instead of a boiling point, although this is because its composition changes: each intermediate mixture has its own, singular boiling point.

The idealized model is accurate in the case of chemically similar liquids, such as benzene and toluene. In other cases, severe deviations from Raoult's law and Dalton's law are observed, most famously in the mixture of ethanol and water. These compounds, when heated together, form an azeotrope, which is when the vapor phase and liquid phase contain the same composition. Although there are computational methods that can be used to estimate the behavior of a mixture of arbitrary components, the only way to obtain accurate vapor–liquid equilibrium data is by measurement.

It is not possible to completely purify a mixture of components by distillation, as this would require each component in the mixture to have a zero partial pressure. If ultra-pure products are the goal, then further chemical separation must be applied. When a binary mixture is vaporized and the other component, e.g., a salt, has zero partial pressure for practical purposes, the process is simpler.

Batch or differential distillation

A batch still showing the separation of A and B.

Heating an ideal mixture of two volatile substances, A and B, with A having the higher volatility, or lower boiling point, in a batch distillation setup (such as in an apparatus depicted in the opening figure) until the mixture is boiling results in a vapor above the liquid that contains a mixture of A and B. The ratio between A and B in the vapor will be different from the ratio in the liquid. The ratio in the liquid will be determined by how the original mixture was prepared, while the ratio in the vapor will be enriched in the more volatile compound, A (due to Raoult's Law, see above). The vapor goes through the condenser and is removed from the system. This, in turn, means that the ratio of compounds in the remaining liquid is now different from the initial ratio (i.e., more enriched in B than in the starting liquid).

The result is that the ratio in the liquid mixture is changing, becoming richer in component B. This causes the boiling point of the mixture to rise, which results in a rise in the temperature in the vapor, which results in a changing ratio of A : B in the gas phase (as distillation continues, there is an increasing proportion of B in the gas phase). This results in a slowly changing ratio of A : B in the distillate.

If the difference in vapour pressure between the two components A and B is large – generally expressed as the difference in boiling points – the mixture in the beginning of the distillation is highly enriched in component A, and when component A has distilled off, the boiling liquid is enriched in component B.

Continuous distillation

Continuous distillation is an ongoing distillation in which a liquid mixture is continuously (without interruption) fed into the process and separated fractions are removed continuously as output streams occur over time during the operation. Continuous distillation produces a minimum of two output fractions, including at least one volatile distillate fraction, which has boiled and been separately captured as a vapor and then condensed to a liquid. There is always a bottoms (or residue) fraction, which is the least volatile residue that has not been separately captured as a condensed vapor.

Continuous distillation differs from batch distillation in the respect that concentrations should not change over time. Continuous distillation can be run at a steady state for an arbitrary amount of time. For any source material of specific composition, the main variables that affect the purity of products in continuous distillation are the reflux ratio and the number of theoretical equilibrium stages, in practice determined by the number of trays or the height of packing. Reflux is a flow from the condenser back to the column, which generates a recycle that allows a better separation with a given number of trays. Equilibrium stages are ideal steps where compositions achieve vapor–liquid equilibrium, repeating the separation process and allowing better separation given a reflux ratio. A column with a high reflux ratio may have fewer stages, but it refluxes a large amount of liquid, giving a wide column with a large holdup. Conversely, a column with a low reflux ratio must have a large number of stages, thus requiring a taller column.

General improvements

Both batch and continuous distillations can be improved by making use of a fractionating column on top of the distillation flask. The column improves separation by providing a larger surface area for the vapor and condensate to come into contact. This helps it remain at equilibrium for as long as possible. The column can even consist of small subsystems ('trays' or 'dishes') which all contain an enriched, boiling liquid mixture, all with their own vapor–liquid equilibrium.

There are differences between laboratory-scale and industrial-scale fractionating columns, but the principles are the same. Examples of laboratory-scale fractionating columns (in increasing efficiency) include

Laboratory procedures

Laboratory scale distillations are almost exclusively run as batch distillations. The device used in distillation, sometimes referred to as a still, consists at a minimum of a reboiler or pot in which the source material is heated, a condenser in which the heated vapor is cooled back to the liquid state, and a receiver in which the concentrated or purified liquid, called the distillate, is collected. Several laboratory scale techniques for distillation exist (see also distillation types).

A completely sealed distillation apparatus could experience extreme and rapidly varying internal pressure, which could cause it to burst open at the joints. Therefore, some path is usually left open (for instance, at the receiving flask) to allow the internal pressure to equalize with atmospheric pressure. Alternatively, a vacuum pump may be used to keep the apparatus at a lower than atmospheric pressure. If the substances involved are air- or moisture-sensitive, the connection to the atmosphere can be made through one or more drying tubes packed with materials that scavenge the undesired air components, or through bubblers that provide a movable liquid barrier. Finally, the entry of undesired air components can be prevented by pumping a low but steady flow of suitable inert gas, like nitrogen, into the apparatus.

Simple distillation

Schematic of a simple distillation setup.

In simple distillation, the vapor is immediately channeled into a condenser. Consequently, the distillate is not pure but rather its composition is identical to the composition of the vapors at the given temperature and pressure. That concentration follows Raoult's law.

As a result, simple distillation is effective only when the liquid boiling points differ greatly (rule of thumb is 25 °C) or when separating liquids from non-volatile solids or oils. For these cases, the vapor pressures of the components are usually different enough that the distillate may be sufficiently pure for its intended purpose.

A cutaway schematic of a simple distillation operation is shown at right. The starting liquid 15 in the boiling flask 2 is heated by a combined hotplate and magnetic stirrer 13 via a silicone oil bath (orange, 14). The vapor flows through a short Vigreux column 3, then through a Liebig condenser 5, is cooled by water (blue) that circulates through ports 6 and 7. The condensed liquid drips into the receiving flask 8, sitting in a cooling bath (blue, 16). The adapter 10 has a connection 9 that may be fitted to a vacuum pump. The components are connected by ground glass joints (gray).

Fractional distillation

For many cases, the boiling points of the components in the mixture will be sufficiently close that Raoult's law must be taken into consideration. Therefore, fractional distillation must be used in order to separate the components by repeated vaporization-condensation cycles within a packed fractionating column. This separation, by successive distillations, is also referred to as rectification.

As the solution to be purified is heated, its vapors rise to the fractionating column. As it rises, it cools, condensing on the condenser walls and the surfaces of the packing material. Here, the condensate continues to be heated by the rising hot vapors; it vaporizes once more. However, the composition of the fresh vapors are determined once again by Raoult's law. Each vaporization-condensation cycle (called a theoretical plate) will yield a purer solution of the more volatile component. In reality, each cycle at a given temperature does not occur at exactly the same position in the fractionating column; theoretical plate is thus a concept rather than an accurate description.

More theoretical plates lead to better separations. A spinning band distillation system uses a spinning band of Teflon or metal to force the rising vapors into close contact with the descending condensate, increasing the number of theoretical plates.

Steam distillation

Like vacuum distillation, steam distillation is a method for distilling compounds which are heat-sensitive. The temperature of the steam is easier to control than the surface of a heating element, and allows a high rate of heat transfer without heating at a very high temperature. This process involves bubbling steam through a heated mixture of the raw material. By Raoult's law, some of the target compound will vaporize (in accordance with its partial pressure). The vapor mixture is cooled and condensed, usually yielding a layer of oil and a layer of water.

Steam distillation of various aromatic herbs and flowers can result in two products; an essential oil as well as a watery herbal distillate. The essential oils are often used in perfumery and aromatherapy while the watery distillates have many applications in aromatherapy, food processing and skin care.

Dimethyl sulfoxide usually boils at 189 °C. Under a vacuum, it distills off into the receiver at only 70 °C.
Perkin triangle distillation setup
  1. Stirrer bar/anti-bumping granules
  2. Still pot
  3. Fractionating column
  4. Thermometer/Boiling point temperature
  5. Teflon tap 1
  6. Cold finger
  7. Cooling water out
  8. Cooling water in
  9. Teflon tap 2
  10. Vacuum/gas inlet
  11. Teflon tap 3
  12. Still receiver

Vacuum distillation

Some compounds have very high boiling points. To boil such compounds, it is often better to lower the pressure at which such compounds are boiled instead of increasing the temperature. Once the pressure is lowered to the vapor pressure of the compound (at the given temperature), boiling and the rest of the distillation process can commence. This technique is referred to as vacuum distillation and it is commonly found in the laboratory in the form of the rotary evaporator.

This technique is also very useful for compounds which boil beyond their decomposition temperature at atmospheric pressure and which would therefore be decomposed by any attempt to boil them under atmospheric pressure.

Short path and molecular distillation

Molecular distillation is vacuum distillation below the pressure of 0.01 torr. 0.01 torr is one order of magnitude above high vacuum, where fluids are in the free molecular flow regime, i.e. the mean free path of molecules is comparable to the size of the equipment. The gaseous phase no longer exerts significant pressure on the substance to be evaporated, and consequently, rate of evaporation no longer depends on pressure. That is, because the continuum assumptions of fluid dynamics no longer apply, mass transport is governed by molecular dynamics rather than fluid dynamics. Thus, a short path between the hot surface and the cold surface is necessary, typically by suspending a hot plate covered with a film of feed next to a cold plate with a line of sight in between. Molecular distillation is used industrially for purification of oils.

Short path vacuum distillation apparatus with vertical condenser (cold finger), to minimize the distillation path;
  1. Still pot with stirrer bar/anti-bumping granules
  2. Cold finger – bent to direct condensate
  3. Cooling water out
  4. cooling water in
  5. Vacuum/gas inlet
  6. Distillate flask/distillate.

Short path distillation is a distillation technique that involves the distillate travelling a short distance, often only a few centimeters, and is normally done at reduced pressure. A classic example would be a distillation involving the distillate travelling from one glass bulb to another, without the need for a condenser separating the two chambers. This technique is often used for compounds which are unstable at high temperatures or to purify small amounts of compound. The advantage is that the heating temperature can be considerably lower (at reduced pressure) than the boiling point of the liquid at standard pressure, and the distillate only has to travel a short distance before condensing. A short path ensures that little compound is lost on the sides of the apparatus. The Kugelrohr apparatus is a kind of short path distillation method which often contains multiple chambers to collect distillate fractions.

Air-sensitive vacuum distillation

Some compounds have high boiling points as well as being air sensitive. A simple vacuum distillation system as exemplified above can be used, whereby the vacuum is replaced with an inert gas after the distillation is complete. However, this is a less satisfactory system if one desires to collect fractions under a reduced pressure. To do this a "cow" or "pig" adaptor can be added to the end of the condenser, or for better results or for very air sensitive compounds a Perkin triangle apparatus can be used.

The Perkin triangle, has means via a series of glass or Teflon taps to allows fractions to be isolated from the rest of the still, without the main body of the distillation being removed from either the vacuum or heat source, and thus can remain in a state of reflux. To do this, the sample is first isolated from the vacuum by means of the taps, the vacuum over the sample is then replaced with an inert gas (such as nitrogen or argon) and can then be stoppered and removed. A fresh collection vessel can then be added to the system, evacuated and linked back into the distillation system via the taps to collect a second fraction, and so on, until all fractions have been collected.

Zone distillation

Zone distillation is a distillation process in a long container with partial melting of refined matter in moving liquid zone and condensation of vapor in the solid phase at condensate pulling in cold area. The process is worked in theory. When zone heater is moving from the top to the bottom of the container then solid condensate with irregular impurity distribution is forming. Then most pure part of the condensate may be extracted as product. The process may be iterated many times by moving (without turnover) the received condensate to the bottom part of the container on the place of refined matter. The irregular impurity distribution in the condensate (that is efficiency of purification) increases with the number of iterations. Zone distillation is the distillation analog of zone recrystallization. Impurity distribution in the condensate is described by known equations of zone recrystallization – with the replacement of the distribution co-efficient k of crystallization - for the separation factor α of distillation.

Other types

  • The process of reactive distillation involves using the reaction vessel as the still. In this process, the product is usually significantly lower-boiling than its reactants. As the product is formed from the reactants, it is vaporized and removed from the reaction mixture. This technique is an example of a continuous vs. a batch process; advantages include less downtime to charge the reaction vessel with starting material, and less workup. Distillation "over a reactant" could be classified as a reactive distillation. It is typically used to remove volatile impurity from the distallation feed. For example, a little lime may be added to remove carbon dioxide from water followed by a second distillation with a little sulfuric acid added to remove traces of ammonia.
  • Catalytic distillation is the process by which the reactants are catalyzed while being distilled to continuously separate the products from the reactants. This method is used to assist equilibrium reactions in reaching completion.
  • Pervaporation is a method for the separation of mixtures of liquids by partial vaporization through a non-porous membrane.
  • Extractive distillation is defined as distillation in the presence of a miscible, high boiling, relatively non-volatile component, the solvent, that forms no azeotrope with the other components in the mixture.
  • Flash evaporation (or partial evaporation) is the partial vaporization that occurs when a saturated liquid stream undergoes a reduction in pressure by passing through a throttling valve or other throttling device. This process is one of the simplest unit operations, being equivalent to a distillation with only one equilibrium stage.
  • Codistillation is distillation which is performed on mixtures in which the two compounds are not miscible. In the laboratory, the Dean-Stark apparatus is used for this purpose to remove water from synthesis products. The Bleidner apparatus is another example with two refluxing solvents.
  • Membrane distillation is a type of distillation in which vapors of a mixture to be separated are passed through a membrane, which selectively permeates one component of mixture. Vapor pressure difference is the driving force. It has potential applications in seawater desalination and in removal of organic and inorganic components.

The unit process of evaporation may also be called "distillation":

  • In rotary evaporation a vacuum distillation apparatus is used to remove bulk solvents from a sample. Typically the vacuum is generated by a water aspirator or a membrane pump.
  • In a Kugelrohr apparatus a short path distillation apparatus is typically used (generally in combination with a (high) vacuum) to distill high boiling (> 300 °C) compounds. The apparatus consists of an oven in which the compound to be distilled is placed, a receiving portion which is outside of the oven, and a means of rotating the sample. The vacuum is normally generated by using a high vacuum pump.

Other uses:

  • Dry distillation or destructive distillation, despite the name, is not truly distillation, but rather a chemical reaction known as pyrolysis in which solid substances are heated in an inert or reducing atmosphere and any volatile fractions, containing high-boiling liquids and products of pyrolysis, are collected. The destructive distillation of wood to give methanol is the root of its common name – wood alcohol.
  • Freeze distillation is an analogous method of purification using freezing instead of evaporation. It is not truly distillation, but a recrystallization where the product is the mother liquor, and does not produce products equivalent to distillation. This process is used in the production of ice beer and ice wine to increase ethanol and sugar content, respectively. It is also used to produce applejack. Unlike distillation, freeze distillation concentrates poisonous congeners rather than removing them; As a result, many countries prohibit such applejack as a health measure. Also, distillation by evaporation can separate these since they have different boiling points.
  • [ Distillation by filtration] In early alchemy and chemistry, otherwise known as natural philosophy, a form of "distillation" by capillary filtration was known as a form of distillation at the time. In this, a series of cups or bowls were set upon a stepped support with a "wick" of cotton or felt-like material, which had been wetted with water or a clear liquid with each step dripping down through the wetted cloth through capillary action in succeeding steps, creating a "purification" of the liquid, leaving solid materials behind in the upper bowls and purifying the succeeding product through capillary action through the moistened cloth. This was called "distillatio" by filtration by those using the method.

Azeotropic process

Interactions between the components of the solution create properties unique to the solution, as most processes entail nonideal mixtures, where Raoult's law does not hold. Such interactions can result in a constant-boiling azeotrope which behaves as if it were a pure compound (i.e., boils at a single temperature instead of a range). At an azeotrope, the solution contains the given component in the same proportion as the vapor, so that evaporation does not change the purity, and distillation does not effect separation. For example, ethyl alcohol and water form an azeotrope of 95.6% at 78.1 °C.

If the azeotrope is not considered sufficiently pure for use, there exist some techniques to break the azeotrope to give a pure distillate. This set of techniques are known as azeotropic distillation. Some techniques achieve this by "jumping" over the azeotropic composition (by adding another component to create a new azeotrope, or by varying the pressure). Others work by chemically or physically removing or sequestering the impurity. For example, to purify ethanol beyond 95%, a drying agent (or desiccant, such as potassium carbonate) can be added to convert the soluble water into insoluble water of crystallization. Molecular sieves are often used for this purpose as well.

Immiscible liquids, such as water and toluene, easily form azeotropes. Commonly, these azeotropes are referred to as a low boiling azeotrope because the boiling point of the azeotrope is lower than the boiling point of either pure component. The temperature and composition of the azeotrope is easily predicted from the vapor pressure of the pure components, without use of Raoult's law. The azeotrope is easily broken in a distillation set-up by using a liquid–liquid separator (a decanter) to separate the two liquid layers that are condensed overhead. Only one of the two liquid layers is refluxed to the distillation set-up.

High boiling azeotropes, such as a 20 percent by weight mixture of hydrochloric acid in water, also exist. As implied by the name, the boiling point of the azeotrope is greater than the boiling point of either pure component.

To break azeotropic distillations and cross distillation boundaries, such as in the DeRosier Problem, it is necessary to increase the composition of the light key in the distillate.

Breaking an azeotrope with unidirectional pressure manipulation

The boiling points of components in an azeotrope overlap to form a band. By exposing an azeotrope to a vacuum or positive pressure, it's possible to bias the boiling point of one component away from the other by exploiting the differing vapor pressure curves of each; the curves may overlap at the azeotropic point, but are unlikely to be remain identical further along the pressure axis either side of the azeotropic point. When the bias is great enough, the two boiling points no longer overlap and so the azeotropic band disappears.

This method can remove the need to add other chemicals to a distillation, but it has two potential drawbacks.

Under negative pressure, power for a vacuum source is needed and the reduced boiling points of the distillates requires that the condenser be run cooler to prevent distillate vapors being lost to the vacuum source. Increased cooling demands will often require additional energy and possibly new equipment or a change of coolant.

Alternatively, if positive pressures are required, standard glassware can not be used, energy must be used for pressurization and there is a higher chance of side reactions occurring in the distillation, such as decomposition, due to the higher temperatures required to effect boiling.

A unidirectional distillation will rely on a pressure change in one direction, either positive or negative.

Pressure-swing distillation

Pressure-swing distillation is essentially the same as the unidirectional distillation used to break azeotropic mixtures, but here both positive and negative pressures may be employed.

This improves the selectivity of the distillation and allows a chemist to optimize distillation by avoiding extremes of pressure and temperature that waste energy. This is particularly important in commercial applications.

One example of the application of pressure-swing distillation is during the industrial purification of ethyl acetate after its catalytic synthesis from ethanol.

Industrial process

Typical industrial distillation towers

Large scale industrial distillation applications include both batch and continuous fractional, vacuum, azeotropic, extractive, and steam distillation. The most widely used industrial applications of continuous, steady-state fractional distillation are in petroleum refineries, petrochemical and chemical plants and natural gas processing plants.

To control and optimize such industrial distillation, a standardized laboratory method, ASTM D86, is established. This test method extends to the atmospheric distillation of petroleum products using a laboratory batch distillation unit to quantitatively determine the boiling range characteristics of petroleum products.

Industrial distillation is typically performed in large, vertical cylindrical columns known as distillation towers or distillation columns with diameters ranging from about 0.65 to 16 metres (2 ft 2 in to 52 ft 6 in) and heights ranging from about 6 to 90 metres (20 to 295 ft) or more. When the process feed has a diverse composition, as in distilling crude oil, liquid outlets at intervals up the column allow for the withdrawal of different fractions or products having different boiling points or boiling ranges. The "lightest" products (those with the lowest boiling point) exit from the top of the columns and the "heaviest" products (those with the highest boiling point) exit from the bottom of the column and are often called the bottoms.

Diagram of a typical industrial distillation tower

Industrial towers use reflux to achieve a more complete separation of products. Reflux refers to the portion of the condensed overhead liquid product from a distillation or fractionation tower that is returned to the upper part of the tower as shown in the schematic diagram of a typical, large-scale industrial distillation tower. Inside the tower, the downflowing reflux liquid provides cooling and condensation of the upflowing vapors thereby increasing the efficiency of the distillation tower. The more reflux that is provided for a given number of theoretical plates, the better the tower's separation of lower boiling materials from higher boiling materials. Alternatively, the more reflux that is provided for a given desired separation, the fewer the number of theoretical plates required. Chemical engineers must choose what combination of reflux rate and number of plates is both economically and physically feasible for the products purified in the distillation column.

Such industrial fractionating towers are also used in cryogenic air separation, producing liquid oxygen, liquid nitrogen, and high purity argon. Distillation of chlorosilanes also enables the production of high-purity silicon for use as a semiconductor.

Section of an industrial distillation tower showing detail of trays with bubble caps

Design and operation of a distillation tower depends on the feed and desired products. Given a simple, binary component feed, analytical methods such as the McCabe–Thiele method or the Fenske equation can be used. For a multi-component feed, simulation models are used both for design and operation. Moreover, the efficiencies of the vapor–liquid contact devices (referred to as "plates" or "trays") used in distillation towers are typically lower than that of a theoretical 100% efficient equilibrium stage. Hence, a distillation tower needs more trays than the number of theoretical vapor–liquid equilibrium stages. A variety of models have been postulated to estimate tray efficiencies.

In modern industrial uses, a packing material is used in the column instead of trays when low pressure drops across the column are required. Other factors that favor packing are: vacuum systems, smaller diameter columns, corrosive systems, systems prone to foaming, systems requiring low liquid holdup, and batch distillation. Conversely, factors that favor plate columns are: presence of solids in feed, high liquid rates, large column diameters, complex columns, columns with wide feed composition variation, columns with a chemical reaction, absorption columns, columns limited by foundation weight tolerance, low liquid rate, large turn-down ratio and those processes subject to process surges.

Large-scale, industrial vacuum distillation column

This packing material can either be random dumped packing (25–76 millimetres (1–3 in) wide) such as Raschig rings or structured sheet metal. Liquids tend to wet the surface of the packing and the vapors pass across this wetted surface, where mass transfer takes place. Unlike conventional tray distillation in which every tray represents a separate point of vapor–liquid equilibrium, the vapor–liquid equilibrium curve in a packed column is continuous. However, when modeling packed columns, it is useful to compute a number of "theoretical stages" to denote the separation efficiency of the packed column with respect to more traditional trays. Differently shaped packings have different surface areas and void space between packings. Both of these factors affect packing performance.

Another factor in addition to the packing shape and surface area that affects the performance of random or structured packing is the liquid and vapor distribution entering the packed bed. The number of theoretical stages required to make a given separation is calculated using a specific vapor to liquid ratio. If the liquid and vapor are not evenly distributed across the superficial tower area as it enters the packed bed, the liquid to vapor ratio will not be correct in the packed bed and the required separation will not be achieved. The packing will appear to not be working properly. The height equivalent to a theoretical plate (HETP) will be greater than expected. The problem is not the packing itself but the mal-distribution of the fluids entering the packed bed. Liquid mal-distribution is more frequently the problem than vapor. The design of the liquid distributors used to introduce the feed and reflux to a packed bed is critical to making the packing perform to it maximum efficiency. Methods of evaluating the effectiveness of a liquid distributor to evenly distribute the liquid entering a packed bed can be found in references. Considerable work has been done on this topic by Fractionation Research, Inc. (commonly known as FRI).

Multi-effect distillation

The goal of multi-effect distillation is to increase the energy efficiency of the process, for use in desalination, or in some cases one stage in the production of ultrapure water. The number of effects is inversely proportional to the kW·h/m3 of water recovered figure, and refers to the volume of water recovered per unit of energy compared with single-effect distillation. One effect is roughly 636 kW·h/m3.

There are many other types of multi-effect distillation processes, including one referred to as simply multi-effect distillation (MED), in which multiple chambers, with intervening heat exchangers, are employed.

In food processing

Beverages

Carbohydrate-containing plant materials are allowed to ferment, producing a dilute solution of ethanol in the process. Spirits such as whiskey and rum are prepared by distilling these dilute solutions of ethanol. Components other than ethanol, including water, esters, and other alcohols, are collected in the condensate, which account for the flavor of the beverage. Some of these beverages are then stored in barrels or other containers to acquire more flavor compounds and characteristic flavors.

Gallery

Retort-in-operation-early-chemistry.png Chemistry in its beginnings used retorts as laboratory equipment exclusively for distillation processes.
Distillation of dry and oxygen-free toluene.jpg A simple set-up to distill dry and oxygen-free toluene.
Vacuum Column.png Diagram of an industrial-scale vacuum distillation column as commonly used in oil refineries
Rotavapor.jpg A rotary evaporator is able to distill solvents more quickly at lower temperatures through the use of a vacuum.
Semi-microscale distillation.jpg Distillation using semi-microscale apparatus. The jointless design eliminates the need to fit pieces together. The pear-shaped flask allows the last drop of residue to be removed, compared with a similarly-sized round-bottom flask The small holdup volume prevents losses. A pig is used to channel the various distillates into three receiving flasks. If necessary the distillation can be carried out under vacuum using the vacuum adapter at the pig.

Operator (computer programming)

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