Hydromethanation

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Hydromethanation, [hahy-droh- meth-uh-ney-shuhn] is the process by which methane (the main constituent of natural gas) is produced through the combination of steam, carbonaceous solids and a catalyst in a fluidized bed reactor. The process, developed over the past 60 years by multiple research groups, enables the highly efficient conversion of coal, petroleum coke and biomass (e.g. switchgrass or wood waste) into clean, pipeline quality methane. [1]

Contents

Chemistry

The chemistry of catalytic hydromethanation involves reacting steam and carbon to produce methane and carbon dioxide, according to the following reaction:

2C + 2H2O -> CH4 + CO2

The process utilizes a specially designed reactor and depends upon a proprietary metal catalyst to promote chemical conversion at the low temperatures where the water gas shift reaction and methanation take place.

When a feedstock treated with the catalyst is introduced into this reactor and mixed with steam, three reactions occur that efficiently convert the feedstock into methane.

Hydromethanation reactions

Steam carbon

C + H2O -> CO + H2

Water-gas shift

CO + H2O -> H2 + CO2

Hydro-gasification

2H2 + C -> CH4

The combination of carbon (C) from the carbon feedstock, water (H2O) from steam, and the catalyst, produces pure methane and a pure stream of carbon dioxide (CO2) which is 100% captured in the system and available for sequestration. The overall reaction is thermally neutral, requiring no addition or removal of heat, making it highly efficient.

The development of hydromethanation is an example of process intensification, where several operations are combined into a single step to improve overall efficiency, reduce maintenance and equipment requirements, and lower capital costs.

Byproducts

In addition to methane, hydromethanation produces a high-purity stream of carbon dioxide (CO2), an odorless, colorless greenhouse gas. This CO2 stream is fully captured in the process and can be prevented from entering the atmosphere using a process called sequestration. The CO2 can be injected into underground oil reserves, through a process called enhanced oil recovery (“EOR”), or geologically sequestered.

Because hydromethanation is a catalytic process that does not rely on the combustion of carbonaceous solids to capture their energy value, it does not produce the nitrogen oxides (NOx), sulfur oxides (SOx) and particulate emissions typically associated with the burning of carbon feedstocks, including certain types of biomass. Due to this quality, it intrinsically captures nearly all of the impurities found in coal and converts them into valuable chemical grade products. Ash, sulfur, nitrogen, and trace metals are all removed using commercial gas clean-up processes and are either safely disposed of or used as raw materials for other products such as sulfuric acid and fertilizer.

Commercialization

GreatPoint Energy, a company founded in 2005 by serial entrepreneur Andrew Perlman, is a forerunner in the development and commercialization of hydromethanation. The company has raised $150 million in venture capital [2] from Dow, AES Corporation, Suncor Energy Inc., Peabody Energy, Advanced Technology Ventures (ATV), Draper Fisher Jurvetson, Kleiner Perkins Caufield & Byers, Khosla Ventures and Citi Capital Advisors (CCA). In May, 2012 GreatPoint Energy and China Wanxiang Holdings closed a $1.25 billion investment and partnership agreement to finance and construct the first phase of a one trillion cubic feet per year coal to natural gas production facility in China. [2] The deal between GreatPoint Energy and Wanxiang was the largest US venture capital investment in 2012. [3]

Related Research Articles

<span class="mw-page-title-main">Haber process</span> Industrial process for ammonia production

The Haber process, also called the Haber–Bosch process, is the main industrial procedure for the production of ammonia. The German chemists Fritz Haber and Carl Bosch developed it in the first decade of the 20th century. The process converts atmospheric nitrogen (N2) to ammonia (NH3) by a reaction with hydrogen (H2) using an iron metal catalyst under high temperatures and pressures. This reaction is slightly exothermic (i.e. it releases energy), meaning that the reaction is favoured at lower temperatures and higher pressures. It decreases entropy, complicating the process. Hydrogen is produced via steam reforming, followed by an iterative closed cycle to react hydrogen with nitrogen to produce ammonia.

<span class="mw-page-title-main">Producer gas</span> Obsolete form of gas fuel

Producer gas is fuel gas that is manufactured by blowing through a coke or coal fire with air and steam simultaneously. It mainly consists of carbon monoxide (CO), hydrogen (H2), as well as substantial amounts of nitrogen (N2). The caloric value of the producer gas is low (mainly because of its high nitrogen content), and the technology is obsolete. Improvements over producer gas, also obsolete, include water gas where the solid fuel is treated intermittently with air and steam and, far more efficiently synthesis gas where the solid fuel is replaced with methane.

Syngas, or synthesis gas, is a mixture of hydrogen and carbon monoxide, in various ratios. The gas often contains some carbon dioxide and methane. It is principally used for producing ammonia or methanol. Syngas is combustible and can be used as a fuel. Historically, it has been used as a replacement for gasoline, when gasoline supply has been limited; for example, wood gas was used to power cars in Europe during WWII.

<span class="mw-page-title-main">Gasification</span> Form of energy conversion

Gasification is a process that converts biomass- or fossil fuel-based carbonaceous materials into gases, including as the largest fractions: nitrogen (N2), carbon monoxide (CO), hydrogen (H2), and carbon dioxide (CO2). This is achieved by reacting the feedstock material at high temperatures (typically >700 °C), without combustion, via controlling the amount of oxygen and/or steam present in the reaction. The resulting gas mixture is called syngas (from synthesis gas) or producer gas and is itself a fuel due to the flammability of the H2 and CO of which the gas is largely composed. Power can be derived from the subsequent combustion of the resultant gas, and is considered to be a source of renewable energy if the gasified compounds were obtained from biomass feedstock.

The Fischer–Tropsch process (FT) is a collection of chemical reactions that converts a mixture of carbon monoxide and hydrogen, known as syngas, into liquid hydrocarbons. These reactions occur in the presence of metal catalysts, typically at temperatures of 150–300 °C (302–572 °F) and pressures of one to several tens of atmospheres. The Fischer–Tropsch process is an important reaction in both coal liquefaction and gas to liquids technology for producing liquid hydrocarbons.

<span class="mw-page-title-main">Steam reforming</span> Method for producing hydrogen and carbon monoxide from hydrocarbon fuels

Steam reforming or steam methane reforming (SMR) is a method for producing syngas (hydrogen and carbon monoxide) by reaction of hydrocarbons with water. Commonly natural gas is the feedstock. The main purpose of this technology is hydrogen production. The reaction is represented by this equilibrium:

In industrial chemistry, coal gasification is the process of producing syngas—a mixture consisting primarily of carbon monoxide (CO), hydrogen, carbon dioxide, methane, and water vapour —from coal and water, air and/or oxygen.

<span class="mw-page-title-main">Sabatier reaction</span> Methanation process of carbon dioxide with hydrogen

The Sabatier reaction or Sabatier process produces methane and water from a reaction of hydrogen with carbon dioxide at elevated temperatures and pressures in the presence of a nickel catalyst. It was discovered by the French chemists Paul Sabatier and Jean-Baptiste Senderens in 1897. Optionally, ruthenium on alumina makes a more efficient catalyst. It is described by the following exothermic reaction:

The water–gas shift reaction (WGSR) describes the reaction of carbon monoxide and water vapor to form carbon dioxide and hydrogen:

<span class="mw-page-title-main">Gas to liquids</span> Conversion of natural gas to liquid petroleum products

Gas to liquids (GTL) is a refinery process to convert natural gas or other gaseous hydrocarbons into longer-chain hydrocarbons, such as gasoline or diesel fuel. Methane-rich gases are converted into liquid synthetic fuels. Two general strategies exist: (i) direct partial combustion of methane to methanol and (ii) Fischer–Tropsch-like processes that convert carbon monoxide and hydrogen into hydrocarbons. Strategy ii is followed by diverse methods to convert the hydrogen-carbon monoxide mixtures to liquids. Direct partial combustion has been demonstrated in nature but not replicated commercially. Technologies reliant on partial combustion have been commercialized mainly in regions where natural gas is inexpensive.

An integrated gasification combined cycle (IGCC) is a technology using a high pressure gasifier to turn coal and other carbon based fuels into pressurized gas—synthesis gas (syngas). It can then remove impurities from the syngas prior to the electricity generation cycle. Some of these pollutants, such as sulfur, can be turned into re-usable byproducts through the Claus process. This results in lower emissions of sulfur dioxide, particulates, mercury, and in some cases carbon dioxide. With additional process equipment, a water-gas shift reaction can increase gasification efficiency and reduce carbon monoxide emissions by converting it to carbon dioxide. The resulting carbon dioxide from the shift reaction can be separated, compressed, and stored through sequestration. Excess heat from the primary combustion and syngas fired generation is then passed to a steam cycle, similar to a combined cycle gas turbine. This process results in improved thermodynamic efficiency, compared to conventional pulverized coal combustion.

Hydrogen gas is produced by several industrial methods. In 2022 less than 1% of hydrogen production was low-carbon. Fossil fuels are the dominant source of hydrogen, for example by steam reforming of natural gas. Other methods of hydrogen production include biomass gasification and methane pyrolysis. Methane pyrolysis and water electrolysis can use any source of electricity including renewable energy. Underground hydrogen is extracted.

A methane reformer is a device based on steam reforming, autothermal reforming or partial oxidation and is a type of chemical synthesis which can produce pure hydrogen gas from methane using a catalyst. There are multiple types of reformers in development but the most common in industry are autothermal reforming (ATR) and steam methane reforming (SMR). Most methods work by exposing methane to a catalyst at high temperature and pressure.

Methanation is the conversion of carbon monoxide and carbon dioxide (COx) to methane (CH4) through hydrogenation. The methanation reactions of COx were first discovered by Sabatier and Senderens in 1902.

Carbon dioxide reforming is a method of producing synthesis gas from the reaction of carbon dioxide with hydrocarbons such as methane with the aid of noble metal catalysts. Synthesis gas is conventionally produced via the steam reforming reaction or coal gasification. In recent years, increased concerns on the contribution of greenhouse gases to global warming have increased interest in the replacement of steam as reactant with carbon dioxide.

<span class="mw-page-title-main">Kim reformer</span>

The Kim reformer is a type of syngas plant invented by Hyun Yong Kim. It is a high temperature furnace, filled with steam and/or carbon dioxide gas and maintaining a thermal equilibrium at a temperature just above 1200 °C, in which the reforming reaction is at its thermodynamic equilibrium and carbonaceous substance is reformed with the highest efficiency.

<span class="mw-page-title-main">GreatPoint Energy</span>

GreatPoint Energy, Inc. is a Chicago, Illinois based energy company that produces natural gas from coal, petroleum coke, and biomass utilizing catalytic hydromethanation. GreatPoint Energy was founded in 2005 by serial entrepreneur Andrew Perlman and his business partners. The company has raised $150 million in venture capital from Dow, AES Corporation, Suncor Energy Inc., Peabody Energy, Advanced Technology Ventures (ATV), Draper Fisher Jurvetson, Kleiner Perkins Caufield & Byers, Khosla Ventures and Citi Capital Advisors (CCA).

Chemical looping reforming (CLR) and gasification (CLG) are the operations that involve the use of gaseous carbonaceous feedstock and solid carbonaceous feedstock, respectively, in their conversion to syngas in the chemical looping scheme. The typical gaseous carbonaceous feedstocks used are natural gas and reducing tail gas, while the typical solid carbonaceous feedstocks used are coal and biomass. The feedstocks are partially oxidized to generate syngas using metal oxide oxygen carriers as the oxidant. The reduced metal oxide is then oxidized in the regeneration step using air. The syngas is an important intermediate for generation of such diverse products as electricity, chemicals, hydrogen, and liquid fuels.

<span class="mw-page-title-main">Carbon capture and utilization</span>

Carbon capture and utilization (CCU) is the process of capturing carbon dioxide (CO2) from industrial processes and transporting it via pipelines to where one intends to use it in industrial processes.

Sorption enhanced water gas shift (SEWGS) is a technology that combines a pre-combustion carbon capture process with the water gas shift reaction (WGS) in order to produce a hydrogen rich stream from the syngas fed to the SEWGS reactor.

References

  1. Fairley, Peter (30 January 2007). "Cheaper Natural Gas from Coal". MIT Technology Review. Retrieved 7 June 2013.
  2. 1 2 Kolodny, Lora (20 February 2012). "Bluer Skies For Shanghai?". The Wall Street Journal. Retrieved 7 June 2013.
  3. Wesoff, Eric (2 January 2013). "GreatPoint Energy and Fisker Automotive win the largest VC rounds in 2012". Green Tech Media. Retrieved 7 June 2013.

See also