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Chemical Reaction Engineering Challenges in the Refining and Petrochemical
e-mail: tdegnan1@nd.edu
Abstract
An emergent bifurcation in hydrocarbon resource and product supply and demand will
provide new challenges and opportunities for the refining and petrochemical industries.
Many of these challenges and opportunities are likely to be addressed through advances
Introduction
Over the next decade, changes in hydrocarbon supply and demand will most assuredly
drive technology advances in the refining and petrochemical sectors. This same assertion
was certainly true in the mid-1900s when growth in product demand drove the addition
of new refineries and new capacity. In the middle of the last century, the goals were
advanced process technologies that scaled-up more effectively and produced more high-
That all changed, as markets matured and projections of peak oil were increasingly
heard the late 1980s, 1990s and at the beginning of the twenty-first century [1,2].
From 1980 to 2000, the number of U.S. petroleum refineries declined by 50%. However,
increased by ~10% (Figure 1). Smaller, less efficient refineries shut down, and the
existing larger, more efficient refineries, expanded to take their place. Refineries that
were linked with petrochemical or lubricant plants had distinct advantages because of
their product diversification and process integration. Advanced process control, improved
beginning of 2014 there were 142 refineries in the U.S. with a total refining capacity of
17.9 million barrels per day. This was one less refinery than at the beginning of 2013.
crude and condensate production from the Bakken formation in North Dakota and the
Eagle Ford formation in south Texas. These were the 20 kBD Dakota Prairie Refining
LLC refinery in Dickenson, ND and the 50 kBD Kinder Morgan condensate processing
facility near Houston, TX. These are the first new refineries constructed in the U.S. since
2008.
Today, gasoline demand along with more stringent environmental regulations and
improved energy efficiency continue to drive most refinery planning. In Europe diesel
rather than gasoline demand drives decisions since diesel continues to power the majority
of Europes light duty vehicles. Globally, the outlook to 2040 is for diminished gasoline
consumption, and for accelerated growth in demand for higher molecular weight fuels
including diesel and jet fuel (Figure 2) [4]. A tightening of vehicle fuel economy
standards coupled with reduced light passenger vehicle demand in developed economies,
and an overall population shift toward large cities is likely to depress gasoline
consumption.
Within the U.S., it is clear that broader application of hydraulic fracturing has
dramatically changed both natural gas and crude supply. Over the past year, the growth
in petroleum production from unconventional resources has largely been responsible for a
decline in the price of crude. Mainly as a result of the additional U.S. hydrocarbon
production, global supply continues to exceeded demand. U.S. crude production has
grown by 72% over the past five years, from 5.6 MBBL/day in 2010 to 9.3 MBBL/day
This growth has been accompanied by a change in the overall crude composition.
Petroleum from reservoirs such as Bakken and Eagle Ford is lighter, more paraffinic, and
lower in sulfur and resid than the more conventional mid-continent crude (Figures 4 and
5a and 5b) [6,7,8]. At the same time, production of heavier, more asphaltenic crude
Implications
The result of North American hydrofracturing and oil shale development has been a
condensate and more heavy residuum in todays crude supply than ever before. This
dumbbell distribution poses both challenges and opportunities for a refining sector that
has, over the past thirty years, geared up for an increasingly heavy slate.
by ~0.9% per year [5]. On the lighter end, basic chemicals volumes, led mainly by
increased demand for light olefins and aromatics, are projected to grow by 2% annually.
Lubricant base stock (Group I and II) capacity is expected to expand over the next 10
are for decreased demand in the lighter base socks and increased demand for gas-to-
The compositional and volumetric changes in supply and demand have several
Fluid catalytic cracking (FCC) units, which have been a mainstay for gasoline
production, are being used to produce more propylene. Less propylene is being
toward ethane and away from naphtha as the feedstock for ethylene production.
FCCs are efficient for converting light paraffinic naphtha to propylene using
isobutane supply increases, butane prices decline, and demand for high-octane
sulfuric acid catalyzed processes. The HF and H2SO4 processes have proved to be
substantial amount of work on the solid acid catalyzed processes [12]. So long as
the refining industry maintains a safe and environmentally responsible record for
operating these units, it is difficult to envision how the current technology will be
replaced. The solid acid catalyzed processes under development (mainly zeolitic)
will have to prove to be at least as durable, and will have to produce gasoline
octane quality better than the highly evolved and optimized HF and H2SO4
environmental regulations may prompt refiners to move away from liquid acids.
Reforming units will be directed toward producing more petrochemical grade
aromatics (BTX) as gasoline demand declines and alkylate, rather than reformate,
greater demand for more diesel and lower sulfur diesel, higher quality lubricants,
and more resid conversion. The projected long term increase in supplies of
natural gas and the decline in natural gas prices has led to a commensurate decline
in the cost of hydrogen. This has also provided greater incentive for refiners to
capacity increases may result from debottlenecking or use of more active and
selective catalysts, which will expand production without capital expense [14]. It
petrochemical production are UOPs PetroFCC TM and RxPro processes [16,17]. The
PetroFCC TM process combines changes in FCC reactor and regenerator design with
changes in process conditions to greatly enhance the production of light olefins and
fresh feed can be achieved. The RxPro process makes use of a multi-stage reactor
useful for converting both vacuum gas oil (VGO) and petroleum resids. The aromatic
byproduct from this process can be sent to an aromatic complex for additional benzene,
The most significant opportunities for technical advances are likely to lie in finding
alternative uses for molecules that would have originally ended up in gasoline. In fact,
the most acute need is in developing catalysts and processes that convert the lighter
Propane, butane, pentane and hexane conversion to higher value products is especially
Light paraffins, which comprise the bulk of natural gas liquids (NGLs) or
condensate, are being produced at much higher than historical rates as a result of
hydrofracturing.
RVP) are projected to tighten forcing more n- and isobutene out of the gasoline
pool, particularly in the summer months and especially in the warmer southern
Ethanol, now typically blended 10 vol% into gasoline in the U.S. per
Reformulated Fuel Standard (RFS), may possibly increase to 15% in some parts
of the U.S. as a result of changes in the RFS. The EPA has allowed 10% ethanol
blends a 1-psi RVP waiver, but has not extended this waiver to 15 vol% ethanol
The most attractive opportunities for use of light paraffins lie in four areas:
1) Producing high quality (high cetane number) diesel range molecules with carbon
2) Producing high viscosity index, highly paraffinic lubricants with carbon numbers
3) Producing more light olefins (propylene, butenes, pentenes, and hexenes) that can
chemicals
The opportunities are listed in descending order of prospective volume demand but
Presently, there are only six commercial routes for upgrading light alkanes to higher
value intermediates:
Once the higher or lower molecular weight olefins, aromatics, and synthesis gas
intermediates are produced, it is a rather simple matter technically to convert these to the
targeted molecules. The challenge then reverts to improving selectivity and improving
separation efficiency.
building more valuable, higher molecular weight alkanes. However, the reaction is
stoichiometric, reacting only one paraffin molecule for every olefin molecule. The
challenge lies in activating light paraffins alone or in a ratio of more than one paraffin per
olefins and selective oxidation to functionalized monomers are both areas that have
received a significant amount of attention in the past. Both routes generally suffer from
poor selectivity because of complicated reaction networks that produce CO and CO2 as a
advances are almost certain to require some combination of novel reactor design, novel
catalytic materials, and perhaps atypical process conditions. For all of the work that has
been directed towards activating methane to produce higher molecular weight products, it
is worth asking whether any of the same approaches or lessons learned can be applied to
Many refiners are adding or expanding petrochemical and lubricant capabilities or are
[19]. More stringent environmental regulations are prompting refiners to add systems
such as low NOx burners in their furnaces and selective catalytic reduction (SCR) units
for their FCC units and furnaces. Advances in process control are allowing refiners to
handle more complexity with the same number of highly trained operating staff.
At the same time, smaller and simpler refineries such as the Dakota Prairie Refining and
Kinder Morgan condensate processing refineries mentioned above are being constructed
in both highly developed and less developed economies. It is reasonable to ask whether
the optimal refining strategy of the future is either small, simple, and part of a widely
a highly concentrated network? There are good arguments for both strategies.
In either case, the need for advanced chemical reactor technology will be strong. There is
a good case to be made for more and more efficient hydroprocessing units to convert the
heavier, more asphaltenic crudes as well as to hydroisomerize the more highly paraffinic
continue to evolve with the need to convert more light naphtha into olefins and aromatic
and heavier, more refractory heavy vacuum gas oil (HVGO) and resids into low sulfur
Moving bed reactor technology, such as that used in UOPs CCR units or Axens Eluxyl
units should continue to evolve not only for production of aromatics and high-octane
gasoline, but also for reactions such as light paraffin dehydrogenation (e.g. UOPs
Oleflex) and perhaps for light paraffin dehydrocyclizaion (e.g., UOPs Cyclar).
molecular weight of the heavier crudes derived from oil sands and heavier Middle
Eastern crudes. It remains a major challenge, for example, to redirect the FCC
unit design away from its original gasoline production focus to one where it
produces more diesel range fuels from the heavier feedstocks. Will we ultimately
concentrations in natural gas reserves while at the same time finding ways to
more efficiently separate heavier more asphaltenic and higher metals resid
molecules from lighter, less asphaltenic, lower metal resid molecules. Cryogenic
separation of light paraffins and olefins is still among the most energy intensive
processes in the refinery. Distillation remains the largest energy consumer in the
refinery. The more than 40,000 distillation columns in North America consume
about 40% of the total energy used to operate plants in the refining and bulk
developing and improving upon simple, intuitive learning models necessary for
We need to do this while continuing to draw upon the experience of engineers who were
benefit from today. The demographics of the petroleum and petrochemical industries are
industry is heavily reliant on its older professionals. Nearly sixty percent are 50 years old
and over creating a worker replacement ratio of 0.25. Stated differently, there is only one
young professional for every four professional approaching retirement. This is cause for
great concern. We need a new generation of talented young professionals to take over
from the retiring workforce that built this industry. [22,23] The same holds true for
funding, which is increasingly focused on less mature, more topical chemical engineering
career opportunities especially for those who combine knowledge of reaction engineering
and catalysis.
Conclusions
Changes in the hydrocarbon resource base, brought about by new extraction technologies
including hydraulic fracturing and oil sand extraction, present many new challenges and
opportunities for the refining and petrochemical industries. There are new opportunities
for light paraffin upgrading especially into high valued petrochemicals, but also into
higher molecular weight fuels, and even lubricants. There are also opportunities for
conversion and hydrogen enrichment of the heavier resid-like molecules into fuels other
than gasoline. The future technology developments will invariably come from combining
new chemical reactor designs with new catalysts or unconventional reaction conditions.
Major technical challenges reside in three areas: (1) improved approaches for controlling
hydrocarbon molecular weight through chemistries that both increase and reduce
molecular weight, (2) more selective separation of both low molecular weight and high
molecular weight hydrocarbons, and (3) development of both more complex and simpler
predictive mathematical models. Industry and academia must work together to ensure
effective transfer of knowledge and expertise from a cohort of retiring chemical reaction
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