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Fig. 1. Technology development timeline for Shells gas-based lubricants.
Shells GTL process is an integrated process that sequentially converts natural gas to syngas, then to
hydrocarbons, and finally to GTL products.1 PurePlus Technology is the Shell-trademarked name in
the US for the proprietary GTL process. An important product of this process is a high-quality base
oil. Shell is the worlds largest producer of GTL base oils at a commercial scale.
Here, the steps involved in the process of converting natural gas to GTL products are described, with
a focus on GTL base oils and fully formulated motor oils.
GTL technology
Editorial comment
-Adrienne Blume
The US and Canada are the worlds largest
shale gas producers, and growing.
The heart of Shells GTL technology is Fischer-Tropsch (FT) synthesis, based on the catalytic
production of paraffin hydrocarbons from carbon monoxide (CO) and hydrogen (H2).2 Natural gas,
the cleanest-burning fossil fuel, was chosen as the preferred hydrocarbon source because it is
affordable, available and environmentally acceptable.
In addition to the FT reaction, there are several other steps involved in the conversion of natural gas
to finished base oils and motor oils, as shown in Fig. 2.
-S. McGinn
Bushton and Conway, Kansas. Located in the
heart of the Midwest is another key NGL
production and storage facility.
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Trace component removal. Organic chlorine and mercury contaminants in natural gas are removed
by adsorbents.
Air separation unit. Cryogenic separation of air is used to obtain oxygen with a purity of
approximately 99.8%.
Gasification process. The gasification process refers to the production of syngas and its subsequent
purification.
Syngas generation. While there are several syngas generation processes,1 non-catalytic partial
oxidation (Fig. 3) is discussed here. Syngas is primarily a mixture of CO and H2. In partial oxidation,
the oxidant (oxygen from the ASU or water) and the hydrocarbon (sweet or desulfurized natural gas)
are allowed to react, without any catalyst, in a refractory clad pressure reactor with top burners at
temperatures of 1,250C1,400C. High-pressure steam, resulting from the raw syngas quench, can
be used to run other assemblies.
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selectivity of desired final products or uncontrollable runaway reactions. In addition to heat removal,
handling the reaction products, such as water, is also necessary to mitigate catalyst deactivation.
Reactor design. Shells GTL process utilizes a multitubular fixed-bed reactor configuration (Fig. 4).
Other reactor designs for FT synthesis are fluidized- and ebulated-bed reactors, slurry-bubble column
reactors and structured reactors.1 The multitublar fixed-bed reaction has several advantages to the
other reactor types, such as higher C5+ selectivity, lower CO2 selectivity, easy scale-up, good
isothermal operation, no catalyst attrition, no intra-particle diffusion limitations and no separation of
catalyst.
Catalyst. The GTL process uses an oxide-supported cobalt (Co) catalyst.1 Co was chosen over an
iron (Fe) catalyst because it shows greater activity under LTFT operation, higher selectivity toward
long-chain hydrocarbons, lower coke formation, lower olefin and oxygenate selectivity, lower CO2
production and higher resistance to deactivation by water.
The use of high surface area and porous metal oxide supports or carriers, in combination with
optimized catalyst size and shape, reduces diffusion-limited reactions and optimizes product
selectivity. The supports also provide hydrothermal stability to the catalyst. Note: While the support
and promoters play an important role, they do not alter the turnover number of the reaction for Co
crystallite sizes of greater than 10 nm.
Following the FT synthesis, the light detergent fraction or n-paraffin fraction (C10C13) is extracted
from the FT product and subsequently hydrogenated. This is a premium feedstock for detergent
production.
Hydrocracking. The syncrude is then subjected to a hydrocracking step, primarily to isomerize
hydrocarbons to improve their cold flow properties. Other reactions include hydrogenation of olefins
and oxygenates. GTL hydrocracking is different from refinery hydrocracking because sulfur- and
nitrogen-containing species and (poly)aromatics are absent.
In terms of reactor design, however, GTL and refinery hydrocrackers are similar. Typically, a multibed trickle-flow adiabatic reactor is used, wherein the hydrogenation of olefins is the fastest reaction,
followed by hydrogenation of oxygenates and isomerization of hydrocarbons. Bifunctional catalysts
with a strong hydrogenation/dehydrogenation function and medium acid-function catalysts are used in
the GTL hydrocracking process.
Distillation. The products of the hydrocracking step are then subjected to atmospheric distillation.
Upon distillation, the boiling fractions obtained are LPG, naphtha (30C175C), kerosine (175C
250C) and gasoil (250C370C). Although not the focus of this article, GTL gasoils are another
important GTL product, since they have extremely high cetane numbers (7075) as a result of their
highly isoparaffinic nature.
Vacuum distillation is applied to the long residue (> 370C) fraction to obtain the raffinate fraction
(370C540C) that is sent to the base oil plant, and a
> 540C fraction that is recycled to the hydrocracker. The base oil plant consists of a unit that
isomerizes n-paraffins and a redistillation unit that converts the raffinate to high-quality base oils.
Finished motor oil. Primarily isoparaffinic in nature and up to 99.5% free of sulfur and nitrogen
impurities, Shells GTL base oils have beneficial properties such as high viscosity indices, good
oxidation stability, low volatility and good cold flow properties. The base oils are then blended with
high-performing additives, such as active cleansers, to produce finished motor oils.
Base oils determine the fundamental properties of the lubricant, and the additives help enhance the
base oil properties and protect the mechanical parts of the engine. Motor oil formulations consist of
approximately 75%90% base oil and 10%25% additives. Therefore, the choice of the correct base
oil has an important impact on the performance of the finished motor oil.
The American Petroleum Institute (API) classifies base oils in different groups based on the minimum
specifications shown in Table 1.
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Shell GTL base oils are classified as Group III base oils, but they exceed minimum API specifications.
Compared to Shell GTL base oils, other Group III base oils are made by refining and chemically
treating crude oil. Fig. 5 shows the difference in composition of Shell GTL base oils to other Group II
and Group III base oils.
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to potentially producing energy-efficient formulations by reducing inertial and bulk viscosity pumping
energy losses and improving the thermal conductivity relative to other Group III base oils.4
Industrial gear oils. Gear oils are primarily base oils with very low additive treat rates. Improved
base oil quality, such as that found in Shell GTL base oils, is highly desirable and manifests as an
improved antioxidant response.4
Takeaway
Shells GTL process has enabled the production of high-quality base oils used in the manufacture of
several passenger car motor oils ranging from products available to the general public to highperformance racing oils.
These base oils will also help in the creation of SAE 0W-16 motor oils for new US Corporate Average
Fuel Economy regulations in the coming years, as Shell works to achieve 54.5 mpg with automobile
original equipment manufacturers. GP
Literature cited
1
Wedlock, D. J., M. Lambert and T. T. Walker, Gas-to-liquids base oils to assist in meeting OEM
requirements 2010 and beyond, 2nd Asia-Pacific Base Oil Conference, Beijing, China, October
2007.
Sravani Gullapalli joined Shell in 2014 as an engineer in the lubricants discovery hub
and is based out of Houston, Texas. Within the hub, Dr. Gullapalli works closely with
the factory plant maintenance oil and alternative fuel compatibility teams as a project
leader. Dr. Gullapalli graduated with a PhD in chemical engineering from Rice
University in December 2013. In 2008, she earned her bachelors degree in chemical
engineering from the National Institute of Technology in Karnataka, India.
Allison Falender is the technology manager for Shells lubricants discovery hub. She
has held multiple roles in biofuels and lubricants technology and has supported different
product groups such as Pennzoil and Rotella. Dr. Falenders team is a global multidisciplinary group of scientists working on several projects that tie together innovation
and product development. She earned her BA degree from Oberlin College in Oberlin,
Ohio, with a double major in biology and sociology. She also holds a PhD in molecular
and cellular biology from Baylor College of Medicine in Houston, Texas.
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