Syngas to gasoline plus
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Syngas to gasoline plus (STG+) is a thermochemical process to convert
natural gas Natural gas (also fossil gas, methane gas, and gas) is a naturally occurring compound of gaseous hydrocarbons, primarily methane (95%), small amounts of higher alkanes, and traces of carbon dioxide and nitrogen, hydrogen sulfide and helium ...
, other gaseous
hydrocarbon In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and Hydrophobe, hydrophobic; their odor is usually fain ...
s or gasified
biomass Biomass is a term used in several contexts: in the context of ecology it means living organisms, and in the context of bioenergy it means matter from recently living (but now dead) organisms. In the latter context, there are variations in how ...
into drop-in fuels, such as gasoline, diesel fuel or jet fuel, and organic solvents.


Process chemistry

This process follows four principal steps in one continuous integrated loop, comprising four fixed bed reactors in a series in which a
syngas 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 ...
is converted to synthetic fuels. The steps for producing high-octane synthetic gasoline are as follows:Introduction to STG+ Technology
''Primus Green Energy'', February 2013. Retrieved: 5 March 2013.
* Methanol Synthesis: Syngas is fed to Reactor 1, the first of four reactors, which converts most of the syngas to methanol when passing through the catalyst bed. *: CO + 2 H2 → *
Dimethyl Ether Dimethyl ether (DME; also known as methoxymethane) is the organic compound with the formula CH3OCH3, (sometimes ambiguously simplified to C2H6O as it is an isomer of ethanol). The simplest ether, it is a colorless gas that is a useful precursor ...
(DME) Synthesis: The methanol-rich gas from Reactor 1 is next fed to Reactor 2, the second STG+ reactor. The methanol is exposed to a
catalyst Catalysis () is the increase in rate of a chemical reaction due to an added substance known as a catalyst (). Catalysts are not consumed by the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycles quick ...
and much of it is converted to DME, which involves a dehydration from methanol to form DME. *: 2 CH3OH → CH3OCH3 + H2O * Gasoline synthesis: The Reactor 2 product gas is next fed to Reactor 3, the third reactor containing the catalyst for conversion of DME to hydrocarbons including paraffins (
alkane In organic chemistry, an alkane, or paraffin (a historical trivial name that also has other meanings), is an acyclic saturated hydrocarbon. In other words, an alkane consists of hydrogen and carbon atoms arranged in a tree structure in whi ...
s),
aromatics Aromatic compounds or arenes are organic compounds "with a chemistry typified by benzene" and "cyclically conjugated." The word "aromatic" originates from the past grouping of molecules based on odor, before their general chemical properties were ...
, naphthenes (
cycloalkane In organic chemistry, the cycloalkanes (also called naphthenes, but distinct from naphthalene) are the ring (chemistry), monocyclic Saturated and unsaturated compounds, saturated hydrocarbons. In other words, a cycloalkane consists only of hydroge ...
s) and small amounts of olefins (
alkene In organic chemistry, an alkene, or olefin, is a hydrocarbon containing a carbon–carbon double bond. The double bond may be internal or at the terminal position. Terminal alkenes are also known as Alpha-olefin, α-olefins. The Internationa ...
s), typically with the carbon number ranging from 6 to 10. * Gasoline Treatment: The fourth reactor provides transalkylation and
hydrogenation Hydrogenation is a chemical reaction between molecular hydrogen (H2) and another compound or element, usually in the presence of a catalyst such as nickel, palladium or platinum. The process is commonly employed to redox, reduce or Saturated ...
treatment to the products coming from Reactor 3. The treatment reduces durene/ isodurene ( tetramethylbenzenes) and trimethylbenzene components that have high freezing points and must be minimized in gasoline. As a result, the synthetic gasoline product has high octane and desirable viscometric properties. * Separator: Finally, the mixture from Reactor 4 is condensed to obtain gasoline. The non-condensed gas and gasoline are separated in a conventional condenser/separator. Most of the non-condensed gas from the product separator becomes recycled gas and is sent back to the feed stream to Reactor 1, leaving the synthetic gasoline product composed of paraffins, aromatics and naphthenes.


Catalysts

The STG+ process uses standard catalysts similar to those used in other gas to liquids technologies, specifically in methanol to gasoline processes. Methanol to gasoline processes favor molecular size- and shape-selective
zeolite Zeolites are a group of several microporous, crystalline aluminosilicate minerals commonly used as commercial adsorbents and catalysts. They mainly consist of silicon, aluminium, oxygen, and have the general formula ・y where is either a meta ...
catalysts, and the STG+ process also utilizes commercially available shape-selective catalysts, such as
ZSM-5 ZSM-5, Zeolite Socony Mobil–5 (framework type MFI from ZSM-5 (five)), is an aluminosilicate zeolite belonging to the pentasil family of zeolites. Its chemical formula is NanAlnSi96–nO192·16H2O (0municipal solid waste Municipal solid waste (MSW), commonly known as trash or garbage in the American English, United States and rubbish in British English, Britain, is a List of waste types, waste type consisting of everyday items that are discarded by the public. ...
. Natural gas and other methane-rich gases, including those produced from municipal waste, are converted into syngas through methane reforming technologies such as steam methane reforming and auto-thermal reforming. Biomass gasification technologies are less established, though several systems being developed utilize fixed bed or
fluidized bed A fluidized bed is a physical phenomenon that occurs when a solid particulate substance (usually present in a holding vessel) is under the right conditions so that it behaves like a fluid. The usual way to achieve a fluidized bed is to pump press ...
reactors.


Comparison to other GTL technologies

Other technologies for syngas to liquid fuels synthesis include the
Fischer–Tropsch process 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 te ...
and the methanol to gasoline processes. Research conducted at Princeton University indicates that methanol to gasoline processes are consistently more cost-effective, both in capital cost and overall cost, than the Fischer–Tropsch process at small, medium and large scales.Richard C. Baliban, Josephine A. Elia, Vern Weekman, and Christodoulos A. Floudas "Process Synthesis of Hybrid Coal, Biomass, and Natural Gas to Liquids via Fischer–Tropsch Synthesis, ZSM-5 Catalytic Conversion, Methanol Synthesis, Methanol-to-Gasoline, and Methanol-to-Olefins/Distillate Technologies" in Computers & Chemical Engineering, 2012, Elsevier. Preliminary studies suggest that the STG+ process is more energetically efficient and the highest yielding methanol to gasoline process.Comparison of STG+ With Other GTL Technologies
''Primus Green Energy'', April 2013. Retrieved: 29 April 2013.


Fischer–Tropsch process

The primary difference between the Fischer–Tropsch process and methanol to gasoline processes such as STG+ are the catalysts used, product types and economics. Generally, the Fischer–Tropsch process favors unselective
cobalt Cobalt is a chemical element; it has Symbol (chemistry), symbol Co and atomic number 27. As with nickel, cobalt is found in the Earth's crust only in a chemically combined form, save for small deposits found in alloys of natural meteoric iron. ...
and
iron Iron is a chemical element; it has symbol Fe () and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, forming much of Earth's o ...
catalysts, while methanol to gasoline technologies favor molecular size- and shape-selective zeolites.Eduardo Falabella Sousa-Aguiar, Fabio Bellot Noronha, and Arnaldo Faro, Jr. "The Main Catalytic Challenges in GTL (Gas-to-Liquids) Processes" in Catalysis Science & Technology, 2011, RSC. In terms of product types, Fischer–Tropsch production has been limited to linear paraffins, such as synthetic crude oil, whereas methanol to gasoline processes can produce aromatics, such as
xylene In organic chemistry, xylene or xylol (; IUPAC name: dimethylbenzene) are any of three organic compounds with the formula . They are derived from the substitution of two hydrogen atoms with methyl groups in a benzene ring; which hydrogens are su ...
and
toluene Toluene (), also known as toluol (), is a substituted aromatic hydrocarbon with the chemical formula , often abbreviated as , where Ph stands for the phenyl group. It is a colorless, water Water is an inorganic compound with the c ...
, and naphthenes and iso-paraffins, such as drop-in gasoline and jet fuel. The main product of the Fischer–Tropsch process, synthetic crude oil, requires additional refining to produce fuel products such as diesel fuel or gasoline. This refining typically adds additional costs, causing some industry leaders to label the economics of commercial-scale Fischer–Tropsch processes as challenging.Broder, John M. and Clifford Krauss
A Big, and Risky, Energy Bet
''The New York Times'', 17 December 2012. Retrieved: 15 April 2013.


Methanol to gasoline

The STG+ technology offers several differentiators that distinguish it from other methanol to gasoline processes. These differences include product flexibility, durene reduction, environmental footprint and capital cost. Traditional methanol to gasoline technologies produce diesel, gasoline or
liquefied petroleum gas Liquefied petroleum gas, also referred to as liquid petroleum gas (LPG or LP gas), is a fuel gas which contains a flammable mixture of hydrocarbon gases, specifically propane, Butane, ''n''-butane and isobutane. It can also contain some ...
.Methanol to Gasoline (MTG) Production of Clean Gasoline from Coal
''ExxonMobil'', December 2009. Retrieved: 30 April 2013.
STG+ produces gasoline, diesel, jet fuel and aromatics, depending on the catalysts used. The STG+ technology also incorporates durene reduction into its core process, meaning that the entire fuel production process requires only two steps: syngas production and gas to liquids synthesis. Other methanol to gasoline processes do not incorporate durene reduction into the core process, and they require the implementation of an additional refining step. Due to the additional number of reactors, traditional methanol to gasoline processes include inefficiencies such as the additional cost and energy loss of condensing and evaporating the methanol prior to feeding it to the durene reduction unit. These inefficiencies can lead to a greater capital cost and environmental footprint than methanol to gasoline processes that use fewer reactors, such as STG+. The STG+ process eliminates multiple condensation and evaporation, and the process converts syngas to liquid transportation fuels directly without producing intermediate liquids. This eliminates the need for storage of two products, including pressure storage for liquefied petroleum gas and storage of liquid methanol. Simplifying a gas to liquids process by combining multiple steps into fewer reactors leads to increased yield and efficiency, enabling less expensive facilities that are more easily scaled.Richard C. Baliban, Josephine A. Elia, and Christodoulos A. Floudas "Novel Natural Gas to Liquids Processes: Process Synthesis and Global Optimization Strategies" in American Institute of Chemical Engineers Journal, 2013, AIChE.


Commercialization

The STG+ technology is currently operating at pre-commercial scale in Hillsborough, New Jersey at a plant owned by alternative fuels company Primus Green Energy. The plant produces approximately 100,000 gallons of high-quality, drop-in gasoline per year directly from natural gas. Further, the company announced the findings of an independent engineer’s report prepared by E3 Consulting, which found that STG+ system and catalyst performance exceeded expectations during plant operation. The pre-commercial demonstration plant has also achieved 720 hours of continuous operation. Primus Green Energy has announced plans to break ground on its first commercial STG+ plant in the second half of 2014, and the company has announced that this plant is expected to produce approximately 27.8 million gallons of fuel annually. In early 2014, the
U.S. Patent and Trademark Office The United States Patent and Trademark Office (USPTO) is an agency in the U.S. Department of Commerce that serves as the national patent office and trademark registration authority for the United States. The USPTO's headquarters are in Alex ...
(USPTO) allowed Primus Green Energy’s patent covering its single-loop STG+ technology.


See also

*
Alternative fuel Alternative fuels, also known as non-conventional and advanced fuels, are fuels derived from sources other than petroleum. Alternative fuels include gaseous fossil fuels like propane, natural gas, methane, and ammonia; biofuels like biodies ...
*
Biogasoline Biogasoline is a type of synthetic fuel, synthetic gasoline produced from biomass (energy), biomass such as algae and plants. Like traditionally petroleum-derived gasoline, biogasoline is made up of hydrocarbons with 6 (hexane) to 12 (dodecane) ca ...
* Biomass to liquid *
Fischer–Tropsch process 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 te ...
*
Gas to liquids Gas to liquids (GTL) is a oil refinery, 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 ...


References

{{reflist, 2 Synthetic fuel technologies Gas technologies