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Chemical reaction engineering challenges in the


refining and petrochemical industries - The
decade ahead

Article in Current Opinion in Chemical Engineering August 2015


DOI: 10.1016/j.coche.2015.09.003

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Chemical Reaction Engineering Challenges in the Refining and Petrochemical

Industries The Decade Ahead

Thomas F. Degnan, Jr.

Department of Chemical and Biomolecular Engineering

University of Notre Dame

Notre Dame, IN 46556

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

in chemical reaction engineering.

Keywords: Reaction engineering, bifurcation, trends, future, refining, petrochemicals

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-

octane gasoline and commodity petrochemicals.

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,

the overall processing capability in terms of primary distillation capacity actually

increased by ~10% (Figure 1). Smaller, less efficient refineries shut down, and the

<Figure 1 should be placed here>

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

models and process intensification facilitated debottlenecking. Technology

improvements continue to allow fewer refineries to produce more gasoline. At the

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.

Yet in 2013 U.S. refining capacity increased by 101,000 BBL/day [3].


Two additional refineries started up at the end of 2014, mainly as a result of increased

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.

<Figure 2 should be placed here>

Impact of Hydraulic Fracturing

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

today (Figure 3) [5].

<Figure 3 should be placed here>

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

primarily from Canadian oil sands has also ramped up.

<Figure 4 should be placed here>

<Figures 5a and 5b should be placed here>

Implications

The result of North American hydrofracturing and oil shale development has been a

bifurcation in the crude composition. Proportionally, there is more light paraffinic

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.

Coincidentally, there is a similar bifurcation in product demand. Diesel consumption is

projected to grow annually by 1% while gasoline demand is actually projected to decline

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

years by approximately 150,000 BBL/day. However, base oil consumption projections

are for decreased demand in the lighter base socks and increased demand for gas-to-

liquid (GTL) and PAO based lubricants [9,10].

The compositional and volumetric changes in supply and demand have several

implications for refining process:

Fluid catalytic cracking (FCC) units, which have been a mainstay for gasoline

production, are being used to produce more propylene. Less propylene is being

produced from conventional ethylene units as chemical manufacturers move

toward ethane and away from naphtha as the feedstock for ethylene production.

FCCs are efficient for converting light paraffinic naphtha to propylene using

ZSM-5 additives. Projections of increased propylene demand are also driving

additions to propane dehydrogenation capacity [11].


Alkylation units (both HF and H2SO4) are or will be running near capacity as

isobutane supply increases, butane prices decline, and demand for high-octane

gasoline remains robust. As interest grows in adding alkylation capacity, there

may be renewed interest in alternatives to the conventional hydrofluoric and

sulfuric acid catalyzed processes. The HF and H2SO4 processes have proved to be

very competitive economically to solid catalyzed alkylation processes, despite a

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

catalyzed processes in order to gain a foothold. Of course, technology is not

always the key motivator in changing processes. New legislation or

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,

is used to increase gasoline octane [13]

Hydrocracking and hydrotreating capacity will continue to expand, driven by

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

invest in expanding hydrotreating and hydrocracking capacity. Some of the

capacity increases may result from debottlenecking or use of more active and

selective catalysts, which will expand production without capital expense [14]. It

is also expected that there will be additional hydroprocessing capacity required to

treat biomass-derived stocks including fast pyrolysis liquids [15] as well as

hydroisomerization of light naphtha for higher octane gasoline [6].

Representative of the shifts in refinery process technology development towards more

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

aromatics. Propylene yields of 12 to 16 wt% (vs. conventional 4 to 6 wt%) based on

fresh feed can be achieved. The RxPro process makes use of a multi-stage reactor

configuration together with reactor technology elements found in conventional

FCC/RFCC designs to generate propylene yields in excess of 20 wt%. The process is

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,

toluene, and p-xylene production.

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

gasoline-range paraffins into higher value chemicals, fuels, or lubricants.

Propane, butane, pentane and hexane conversion to higher value products is especially

attractive for several reasons:

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.

U.S. Government restrictions on gasoline volatility (Reid Vapor Pressure or

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

and southwestern states.

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

blends. If 15 vol% ethanol blends become widespread, even more light

hydrocarbons will be forced from the gasoline pool.

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

numbers from C14 to C20.

2) Producing high viscosity index, highly paraffinic lubricants with carbon numbers

from C24 to C100

3) Producing more light olefins (propylene, butenes, pentenes, and hexenes) that can

be used as petrochemical building blocks for polymers, fuels, and specialty

chemicals

4) Producing specialty oxygenates (alcohols, ethers, ketones, aldehydes, carboxylic

acids, etc.), amines, thiols and mercaptans.

The opportunities are listed in descending order of prospective volume demand but

increasing order of prospective value uplift.

Presently, there are only six commercial routes for upgrading light alkanes to higher

value intermediates:

1) Dehydrogenation to produce the corresponding light olefins

2) Hydroisomerization of C4 to C7 n-paraffins to isoparaffins for production of

higher octane gasoline

3) Alkylation with a light olefin, a route used commercially to produce gasoline

range molecules from butanes and increasingly from pentanes.

4) Dehydrocyclization to produce primarily benzene, toluene, xylenes, and

hydrogen. This is commercially practiced in UOPs Cyclar process


5) Partial oxidation to produce syngas that can be further reacted to higher MW

paraffins through the Fischer-Tropsch reaction or to methanol

6) Free radical cracking, typically conducted at higher temperatures, and most

commonly to produce ethylene

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.

It is difficult to improve economically upon conventional isoparaffin-olefin alkylation for

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

olefin to produce higher molecular weight compounds. Oxidative dehydrogenation to

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

result of consecutive reactions involving deep oxidation of intermediates.

Similar to UOPs development of its PetroFCC TM and RxPro processes, future

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

propane, butanes, pentanes or hexanes? Clearly, there is incentive to improve upon

current light paraffin activation routes [18].

Bifurcation Trends and Challenges

In addition to the previously described bifurcation of hydrocarbon resources

(feedstocks) and products, we are also confronting a bifurcation in manufacturing

(Figure 6). Refineries in highly developed economies are increasing in complexity.

<Figure 6 should be placed here>

Many refiners are adding or expanding petrochemical and lubricant capabilities or are

attempting to improve energy efficiency via addition or expansion of cogeneration units

[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

distributed fuels-petrochemical-energy production network or large, complex, and part of

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

unconventional crudes. We should expect FCC reactor and regenerator technology to

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

gasoline and diesel.

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).

The bifurcated technical challenges (Figure 7) are threefold:


1. Develop process technology to more efficiently build-up molecular weight from

the lighter hydrocarbons derived from condensate and unconventional crudes

while also developing process technology to more efficiently reduce the

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

be able to develop reactor technologies that have the versatility to process a

broader range of feedstocks?

2. Identify and develop more efficient technologies for separating light

hydrocarbons from, for example CO2, which is sometimes found in large

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

chemical industries [20]. Recent strides in the development of inorganic

membranes (e.g., zeolitic and metal organic framework (MOFs)) as well as

durable polymeric membranes may provide the keys. Using process


intensification strategies, will we see more technologies that allow simultaneous

reaction and separation for processes?

3. Continue to progress the predictive and simulation capabilities of more

sophisticated models, such as the Structure-Oriented Lumping (SOL)

compositional models developed by ExxonMobil [21], while simultaneously

developing and improving upon simple, intuitive learning models necessary for

helping operators and less experienced or new engineers understand the

fundamentals of chemical reactor engineering. For example, will it be possible to

combine computational fluid dynamics (CFD) models with compositional

reaction models to improve reactor design and operation?

<Figure 7 should be placed here>

We must also continue to develop a new generation of experts in reaction engineering.

We need to do this while continuing to draw upon the experience of engineers who were

involved in the development and commercialization of process technologies that we

benefit from today. The demographics of the petroleum and petrochemical industries are

challenging. According to several recent studies the US petroleum and petrochemical

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

industrial chemical reactor engineering expertise. Diminished university research

funding, which is increasingly focused on less mature, more topical chemical engineering

subjects, is part of the challenge. However, it is important to continue to emphasize the

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

engineers to the next generation of experts.

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