Steam reforming
Encyclopedia
Fossil fuel reforming is a method of producing hydrogen
or other useful products from fossil fuels such as natural gas
. This is achieved in a processing device called a reformer which reacts steam at high temperature with the fossil fuel. The steam methane reformer
is widely used in industry to make hydrogen
. There is also interest in the development of much smaller units based on similar technology to produce hydrogen
as a feedstock for fuel cells. Small-scale steam reforming units to supply fuel cells are currently the subject of research and development, typically involving the reforming of methanol
or natural gas
but other fuels are also being considered such as propane
, gasoline
, autogas
, diesel fuel, and ethanol
.
or syngas
sometimes referred to as steam methane reforming (SMR) is the most common method of producing commercial bulk hydrogen as well as the hydrogen used in the industrial synthesis of ammonia
. It is also the least expensive method. At high temperatures (700 – 1100 °C) and in the presence of a metal
-based catalyst (nickel
), steam reacts with methane to yield carbon monoxide
and hydrogen. These two reactions are reversible in nature.
Additional hydrogen can be recovered by a lower-temperature gas-shift reaction
with the carbon monoxide
produced. The reaction is summarized by:
The first reaction is strongly endothermic
(consumes heat), the second reaction is mildly exothermic
(produces heat).
The United States
produces nine million tons of hydrogen per year, mostly with steam reforming of natural gas. The worldwide ammonia production, using hydrogen derived from steam reforming, was 109 million metric tonnes in 2004.
This SMR process is quite different from and not to be confused with catalytic reforming
of naphtha
, an oil refinery
process that also produces significant amounts of hydrogen along with high octane
gasoline
.
The efficiency of the process is approximately 65% to 75%.
tank and a steam reforming unit would replace the bulky pressurized hydrogen tank
s that would otherwise be necessary. This might mitigate the distribution problems
associated with hydrogen vehicles., however the major market players discarded the approach of on-board reforming as unpractical.
rather than distributed release, carbon capture and storage
becomes a possibility, which would prevent the carbon dioxide's release to the atmosphere, while adding to the cost of the process.
The cost of hydrogen production by reforming fossil fuels depends on the scale at which it is done, the capital cost of the reformer and the efficiency of the unit, so that whilst it may cost only a few dollars per kilogram of hydrogen at industrial scale, it could be more expensive at the smaller scale needed for fuel cells. Recently, a Polish company Bioleux Polska has been advertising renewable hydrogen (RH2) plasma reformers, producing RH2 at under $2 per kilogram , and available for lightweight mobile applications using vegetable oil or glycerol as feedstock.
Hydrogen
Hydrogen is the chemical element with atomic number 1. It is represented by the symbol H. With an average atomic weight of , hydrogen is the lightest and most abundant chemical element, constituting roughly 75% of the Universe's chemical elemental mass. Stars in the main sequence are mainly...
or other useful products from fossil fuels such as natural gas
Natural gas
Natural gas is a naturally occurring gas mixture consisting primarily of methane, typically with 0–20% higher hydrocarbons . It is found associated with other hydrocarbon fuel, in coal beds, as methane clathrates, and is an important fuel source and a major feedstock for fertilizers.Most natural...
. This is achieved in a processing device called a reformer which reacts steam at high temperature with the fossil fuel. The steam methane reformer
Methane reformer
A methane refomer is a device based on steam reforming or autothermal reforming and is a type of chemical synthesis, which can produce pure hydrogen gas from natural gas using a catalyst. There are two natural gas reformer technologies — autothermal reforming and steam methane reforming...
is widely used in industry to make hydrogen
Hydrogen
Hydrogen is the chemical element with atomic number 1. It is represented by the symbol H. With an average atomic weight of , hydrogen is the lightest and most abundant chemical element, constituting roughly 75% of the Universe's chemical elemental mass. Stars in the main sequence are mainly...
. There is also interest in the development of much smaller units based on similar technology to produce hydrogen
Hydrogen
Hydrogen is the chemical element with atomic number 1. It is represented by the symbol H. With an average atomic weight of , hydrogen is the lightest and most abundant chemical element, constituting roughly 75% of the Universe's chemical elemental mass. Stars in the main sequence are mainly...
as a feedstock for fuel cells. Small-scale steam reforming units to supply fuel cells are currently the subject of research and development, typically involving the reforming of methanol
Methanol
Methanol, also known as methyl alcohol, wood alcohol, wood naphtha or wood spirits, is a chemical with the formula CH3OH . It is the simplest alcohol, and is a light, volatile, colorless, flammable liquid with a distinctive odor very similar to, but slightly sweeter than, ethanol...
or natural gas
Natural gas
Natural gas is a naturally occurring gas mixture consisting primarily of methane, typically with 0–20% higher hydrocarbons . It is found associated with other hydrocarbon fuel, in coal beds, as methane clathrates, and is an important fuel source and a major feedstock for fertilizers.Most natural...
but other fuels are also being considered such as propane
Propane
Propane is a three-carbon alkane with the molecular formula , normally a gas, but compressible to a transportable liquid. A by-product of natural gas processing and petroleum refining, it is commonly used as a fuel for engines, oxy-gas torches, barbecues, portable stoves, and residential central...
, gasoline
Gasoline
Gasoline , or petrol , is a toxic, translucent, petroleum-derived liquid that is primarily used as a fuel in internal combustion engines. It consists mostly of organic compounds obtained by the fractional distillation of petroleum, enhanced with a variety of additives. Some gasolines also contain...
, autogas
Autogas
Autogas is the common name for liquefied petroleum gas when it is used as a fuel in internal combustion engines in vehicles as well as in stationary applications such as generators. It is a mixture of propane and butane....
, diesel fuel, and ethanol
Ethanol
Ethanol, also called ethyl alcohol, pure alcohol, grain alcohol, or drinking alcohol, is a volatile, flammable, colorless liquid. It is a psychoactive drug and one of the oldest recreational drugs. Best known as the type of alcohol found in alcoholic beverages, it is also used in thermometers, as a...
.
History
- 1923 - The first synthetic methanolMethanolMethanol, also known as methyl alcohol, wood alcohol, wood naphtha or wood spirits, is a chemical with the formula CH3OH . It is the simplest alcohol, and is a light, volatile, colorless, flammable liquid with a distinctive odor very similar to, but slightly sweeter than, ethanol...
was produced by BASFBASFBASF SE is the largest chemical company in the world and is headquartered in Germany. BASF originally stood for Badische Anilin- und Soda-Fabrik . Today, the four letters are a registered trademark and the company is listed on the Frankfurt Stock Exchange, London Stock Exchange, and Zurich Stock...
in LeunaLeunaLeuna is a town in the Saalekreis, Saxony-Anhalt, eastern Germany, south of Merseburg and Halle. It is known for the Leunawerke , at 13 km2 one of the biggest chemical industrial complexes in Germany, where a very wide range of chemicals and plastics is produced...
making use of hydrogen derived from lignite.
Industrial reforming
Steam reforming of natural gasNatural gas
Natural gas is a naturally occurring gas mixture consisting primarily of methane, typically with 0–20% higher hydrocarbons . It is found associated with other hydrocarbon fuel, in coal beds, as methane clathrates, and is an important fuel source and a major feedstock for fertilizers.Most natural...
or syngas
Syngas
Syngas is the name given to a gas mixture that contains varying amounts of carbon monoxide and hydrogen. Examples of production methods include steam reforming of natural gas or liquid hydrocarbons to produce hydrogen, the gasification of coal, biomass, and in some types of waste-to-energy...
sometimes referred to as steam methane reforming (SMR) is the most common method of producing commercial bulk hydrogen as well as the hydrogen used in the industrial synthesis of ammonia
Ammonia production
Because of its many uses, ammonia is one of the most highly-produced inorganic chemicals. There are numerous large-scale ammonia production plants worldwide, producing a total of 131,000,000 metric tons of ammonia in 2010. China produced 32.1% of the worldwide production, followed by India with...
. It is also the least expensive method. At high temperatures (700 – 1100 °C) and in the presence of a metal
Metal
A metal , is an element, compound, or alloy that is a good conductor of both electricity and heat. Metals are usually malleable and shiny, that is they reflect most of incident light...
-based catalyst (nickel
Nickel
Nickel is a chemical element with the chemical symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel belongs to the transition metals and is hard and ductile...
), steam reacts with methane to yield carbon monoxide
Carbon monoxide
Carbon monoxide , also called carbonous oxide, is a colorless, odorless, and tasteless gas that is slightly lighter than air. It is highly toxic to humans and animals in higher quantities, although it is also produced in normal animal metabolism in low quantities, and is thought to have some normal...
and hydrogen. These two reactions are reversible in nature.
- CH4MethaneMethane is a chemical compound with the chemical formula . It is the simplest alkane, the principal component of natural gas, and probably the most abundant organic compound on earth. The relative abundance of methane makes it an attractive fuel...
+ H2OWaterWater is a chemical substance with the chemical formula H2O. A water molecule contains one oxygen and two hydrogen atoms connected by covalent bonds. Water is a liquid at ambient conditions, but it often co-exists on Earth with its solid state, ice, and gaseous state . Water also exists in a...
→ COCarbon monoxideCarbon monoxide , also called carbonous oxide, is a colorless, odorless, and tasteless gas that is slightly lighter than air. It is highly toxic to humans and animals in higher quantities, although it is also produced in normal animal metabolism in low quantities, and is thought to have some normal...
+ 3 H2HydrogenHydrogen is the chemical element with atomic number 1. It is represented by the symbol H. With an average atomic weight of , hydrogen is the lightest and most abundant chemical element, constituting roughly 75% of the Universe's chemical elemental mass. Stars in the main sequence are mainly...
Additional hydrogen can be recovered by a lower-temperature gas-shift reaction
Water gas shift reaction
The water-gas shift reaction is a chemical reaction in which carbon monoxide reacts with water vapor to form carbon dioxide and hydrogen:The water-gas shift reaction is an important industrial reaction. It is often used in conjunction with steam reforming of methane or other hydrocarbons, which is...
with the carbon monoxide
Carbon monoxide
Carbon monoxide , also called carbonous oxide, is a colorless, odorless, and tasteless gas that is slightly lighter than air. It is highly toxic to humans and animals in higher quantities, although it is also produced in normal animal metabolism in low quantities, and is thought to have some normal...
produced. The reaction is summarized by:
- COCarbon monoxideCarbon monoxide , also called carbonous oxide, is a colorless, odorless, and tasteless gas that is slightly lighter than air. It is highly toxic to humans and animals in higher quantities, although it is also produced in normal animal metabolism in low quantities, and is thought to have some normal...
+ H2OWaterWater is a chemical substance with the chemical formula H2O. A water molecule contains one oxygen and two hydrogen atoms connected by covalent bonds. Water is a liquid at ambient conditions, but it often co-exists on Earth with its solid state, ice, and gaseous state . Water also exists in a...
→ CO2Carbon dioxideCarbon dioxide is a naturally occurring chemical compound composed of two oxygen atoms covalently bonded to a single carbon atom...
+ H2HydrogenHydrogen is the chemical element with atomic number 1. It is represented by the symbol H. With an average atomic weight of , hydrogen is the lightest and most abundant chemical element, constituting roughly 75% of the Universe's chemical elemental mass. Stars in the main sequence are mainly...
The first reaction is strongly endothermic
Endothermic
In thermodynamics, the word endothermic describes a process or reaction in which the system absorbs energy from the surroundings in the form of heat. Its etymology stems from the prefix endo- and the Greek word thermasi,...
(consumes heat), the second reaction is mildly exothermic
Exothermic
In thermodynamics, the term exothermic describes a process or reaction that releases energy from the system, usually in the form of heat, but also in the form of light , electricity , or sound...
(produces heat).
The United States
United States
The United States of America is a federal constitutional republic comprising fifty states and a federal district...
produces nine million tons of hydrogen per year, mostly with steam reforming of natural gas. The worldwide ammonia production, using hydrogen derived from steam reforming, was 109 million metric tonnes in 2004.
This SMR process is quite different from and not to be confused with catalytic reforming
Catalytic reforming
Catalytic reforming is a chemical process used to convert petroleum refinery naphthas, typically having low octane ratings, into high-octane liquid products called reformates which are components of high-octane gasoline...
of naphtha
Naphtha
Naphtha normally refers to a number of different flammable liquid mixtures of hydrocarbons, i.e., a component of natural gas condensate or a distillation product from petroleum, coal tar or peat boiling in a certain range and containing certain hydrocarbons. It is a broad term covering among the...
, an oil refinery
Oil refinery
An oil refinery or petroleum refinery is an industrial process plant where crude oil is processed and refined into more useful petroleum products, such as gasoline, diesel fuel, asphalt base, heating oil, kerosene, and liquefied petroleum gas...
process that also produces significant amounts of hydrogen along with high octane
Octane rating
Octane rating or octane number is a standard measure of the anti-knock properties of a motor or aviation fuel. The higher the octane number, the more compression the fuel can withstand before detonating...
gasoline
Gasoline
Gasoline , or petrol , is a toxic, translucent, petroleum-derived liquid that is primarily used as a fuel in internal combustion engines. It consists mostly of organic compounds obtained by the fractional distillation of petroleum, enhanced with a variety of additives. Some gasolines also contain...
.
The efficiency of the process is approximately 65% to 75%.
Advantages of reforming for supplying fuel cells
Steam reforming of gaseous hydrocarbons is seen as a potential way to provide fuel for fuel cells. The basic idea for vehicle on-board reforming is that for example a methanolMethanol
Methanol, also known as methyl alcohol, wood alcohol, wood naphtha or wood spirits, is a chemical with the formula CH3OH . It is the simplest alcohol, and is a light, volatile, colorless, flammable liquid with a distinctive odor very similar to, but slightly sweeter than, ethanol...
tank and a steam reforming unit would replace the bulky pressurized hydrogen tank
Hydrogen tank
A Hydrogen tank is used for hydrogen storage. The first type IV hydrogen tanks for compressed hydrogen at 700 Bar were demonstrated in 2001, the first fuel cell vehicles on the road with type IV tanks are the Toyota FCHV, Mercedes-Benz F-Cell and the HydroGen4.At the hydrogen station Hamburg...
s that would otherwise be necessary. This might mitigate the distribution problems
Hydrogen highway
A hydrogen highway is a chain of hydrogen-equipped filling stations and other infrastructure along a road or highway which allow hydrogen powered cars to travel. It is an element of the hydrogen infrastructure that is generally assumed to be a pre-requisite for mass utilization of hydrogen cars....
associated with hydrogen vehicles., however the major market players discarded the approach of on-board reforming as unpractical.
Disadvantages of reforming for supplying fuel cells
The reformer–fuel-cell system is still being researched but in the near term, systems would continue to run on existing fuels, such as natural gas or gasoline or diesel. However, there is an active debate about whether using these fuels to make hydrogen is beneficial while global warming is an issue. Fossil fuel reforming does not eliminate carbon dioxide release into the atmosphere but reduces the carbon dioxide emissions as compared to the burning of conventional fuels due to increased efficiency. However, by turning the release of carbon dioxide into a point sourcePoint source
A point source is a localised, relatively small source of something.Point source may also refer to:*Point source , a localised source of pollution**Point source water pollution, water pollution with a localized source...
rather than distributed release, carbon capture and storage
Carbon capture and storage
Carbon capture and storage , alternatively referred to as carbon capture and sequestration, is a technology to prevent large quantities of from being released into the atmosphere from the use of fossil fuel in power generation and other industries. It is often regarded as a means of mitigating...
becomes a possibility, which would prevent the carbon dioxide's release to the atmosphere, while adding to the cost of the process.
The cost of hydrogen production by reforming fossil fuels depends on the scale at which it is done, the capital cost of the reformer and the efficiency of the unit, so that whilst it may cost only a few dollars per kilogram of hydrogen at industrial scale, it could be more expensive at the smaller scale needed for fuel cells. Recently, a Polish company Bioleux Polska has been advertising renewable hydrogen (RH2) plasma reformers, producing RH2 at under $2 per kilogram , and available for lightweight mobile applications using vegetable oil or glycerol as feedstock.
Current problems with reformers supplying fuel cells
However, there are several challenges associated with this technology:- The reforming reaction takes place at high temperatures, making it slow to start up and requiring costly high temperature materials.
- SulfurSulfurSulfur or sulphur is the chemical element with atomic number 16. In the periodic table it is represented by the symbol S. It is an abundant, multivalent non-metal. Under normal conditions, sulfur atoms form cyclic octatomic molecules with chemical formula S8. Elemental sulfur is a bright yellow...
compounds present in the fuel poison certain catalysts, making it difficult to run this type of system from ordinary gasolineGasolineGasoline , or petrol , is a toxic, translucent, petroleum-derived liquid that is primarily used as a fuel in internal combustion engines. It consists mostly of organic compounds obtained by the fractional distillation of petroleum, enhanced with a variety of additives. Some gasolines also contain...
. Some new technologies have overcome this challenge, however, with sulfur-tolerant catalysts. - Low temperature polymer fuel cell membranes can be poisoned by the carbon monoxideCarbon monoxideCarbon monoxide , also called carbonous oxide, is a colorless, odorless, and tasteless gas that is slightly lighter than air. It is highly toxic to humans and animals in higher quantities, although it is also produced in normal animal metabolism in low quantities, and is thought to have some normal...
(CO) produced by the reactor, making it necessary to include complex CO-removal systems. Solid oxide fuel cells (SOFC) and Molten carbonate fuel cells (MCFC) do not have this problem, but operate at higher temperatures, slowing start-up time, and requiring costly materials and bulky insulation. - The thermodynamic efficiency of the process is between 70% and 85% (LHV basis) depending on the purity of the hydrogen product.
- The catalyst in low temperature fuel cells is based on platinumPlatinumPlatinum is a chemical element with the chemical symbol Pt and an atomic number of 78. Its name is derived from the Spanish term platina del Pinto, which is literally translated into "little silver of the Pinto River." It is a dense, malleable, ductile, precious, gray-white transition metal...
, and is hence very expensive. A typical automotive fuel cell stack prototype (100 kW) contains 20-30g of platinum metal in the form of nano-particles supported on carbon blackCarbon blackCarbon black is a material produced by the incomplete combustion of heavy petroleum products such as FCC tar, coal tar, ethylene cracking tar, and a small amount from vegetable oil. Carbon black is a form of amorphous carbon that has a high surface-area-to-volume ratio, although its...
.
External links
- "New catalyst boosts hydrogen as transport fuel". By Alok Jha. August 21, 2008. The GuardianThe GuardianThe Guardian, formerly known as The Manchester Guardian , is a British national daily newspaper in the Berliner format...
. - "Hydrogen Production - Steam Methane Reforming (SMR)"
See also
- BiogasBiogasBiogas typically refers to a gas produced by the biological breakdown of organic matter in the absence of oxygen. Organic waste such as dead plant and animal material, animal dung, and kitchen waste can be converted into a gaseous fuel called biogas...
- Cracking (chemistry)Cracking (chemistry)In petroleum geology and chemistry, cracking is the process whereby complex organic molecules such as kerogens or heavy hydrocarbons are broken down into simpler molecules such as light hydrocarbons, by the breaking of carbon-carbon bonds in the precursors. The rate of cracking and the end products...
- Hydrogen pinchHydrogen pinchHydrogen pinch analysis is a hydrogen management method that originates from the concept of heat pinch analysis. HPA is a systematic technique for reducing hydrogen consumption and hydrogen generation through integration of hydrogen-using activities or processes in the petrochemical industry,...
- Hydrogen technologiesHydrogen technologiesHydrogen technologies are technologies that relate to the production and use of hydrogen. Hydrogen technologies are applicable for many uses....
- Lane hydrogen producerLane hydrogen producerThe Lane hydrogen producer was an apparatus for hydrogen production based on the steam-iron process and water gas invented in 1903 by Howard Lane.-History:...
- PROXPROXPROX is an acronym for PReferential OXidation, and refers to the preferential oxidation of a gas on a catalyst.The catalyser preferentially oxidises carbon monoxide using a heterogeneous catalyst placed upon a ceramic support...
- Reformer sponge iron cycleReformer sponge iron cycleThe reformer sponge iron cycle is a two step cycle to produce hydrogen from hydrocarbon fuels based on the sponge iron reaction and steam.-Process description:...
- Timeline of hydrogen technologiesTimeline of hydrogen technologiesTimeline of hydrogen technologies — A timeline of the history of hydrogen technology.-1600s:* 1625 - First description of hydrogen by Johann Baptista van Helmont...