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CO2 MANAGEMENT IN REFINERIES

Graham Phillips
Technology Manager Refining / E. Hemisphere
Foster Wheeler Energy Limited
Reading, UK
Graham_Phillips@fwuk.fwc.com

GASIFICATION V
NOORDWIJK, HOLLAND
April 2002
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Introduction

Production of CO2 globally has been brought into sharp focus in recent times through
declarations such as the Kyoto accord, and also by industry leaders committing to
tangible reductions.

In essence, the Kyoto accord distilled a global problem into a national one, by setting
emission targets for greenhouse gases compared with a baseline 1990 level, with a view
to pegging and reducing global emissions.

How individual nations, economic communities (such as the EU) and industry react to the
growing pressures to reduce CO2 is still to be formulated and ratified. A key element in
the debate is whether specific industries should be targeted and whether CO2 trading
should be allowed across national boundaries and/or industries.

The energy sector, including refining, is likely to feature in any legislation aimed at
curbing CO2 emissions. However, in this case the refiner may see real benefits and
opportunities in adopting a CO2 management and reduction strategy, in order to;

• Be seen as a “good neighbour”

• Benefit from some of the economic gains of CO2 reductions (e.g. energy
conservation, CO2 utilisation).

• Apply technologies, such as gasification, which allow heavy residue destruction,

relatively easy CO2 capture and other environmental benefits.

This paper discusses how CO2 can be managed on the refinery and the potential that
gasification has to significantly reduce CO2 emissions.

Sources of refinery CO2 Emissions

Figure 1: typical breakdown of CO2 emissions in the oil industry on the basis of MWth
of energy delivered.

91.72%
Oil products
combustion
91.72%

Refinery
4.95%
4.95%
1.03%
Product shipping 2.29%
Crude shipping
2.29%
1.03%

Approximately 90% of CO2 emissions comes from combustion of the final product, with
the refining activity itself contributing around 5%.

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Legislation and fiscal pressures can be expected to target the end product user and this
is already taking place. For example, in many countries diesel fuel receives a lower rate
of taxation, compared to gasoline, because of diesels lower CO2 generation per kilometre
travelled. This “dash to diesel” is contributing to a significant shift in product demand. In
Europe, for example, the diesel deficit is expected to grow from the current 10 million
tonnes per annum to around 45 million tonnes per annum by 2010.

Although, a relatively small contributor to CO2 emissions in the oil sector overall, the
refinery can be expected to come under pressure to reduce emissions. Legislators
appear to group the refining activity with the power generation sector and other stationary
sources.

The key to understanding the emissions from the refinery is to understand the carbon
balance of the refinery:

Carbon in Carbon in Carbon in

= +
Feedstock Product Emission

The refinery is essentially a carbon / hydrogen manipulator, tailoring and reshaping

molecules and boiling ranges to meet the performance needs of particular fuels.

All emissions from the refinery itself originate from the feedstocks used. These
feedstocks are the main crude oil(s) to be processed, plus other imported feedstocks
such as condensates or VGOs, and supplementary natural gas for fuel or hydrogen
plants. Carbon is found in the products produced (gasoline, diesel etc), with the balance
emitted into the environment. Whilst most carbon emissions from the refinery will be in
the form of CO2, there are other emissions, such as VOCs, coke on catalysts (which
could be landfilled) and other minor emissions. Shadow emissions from energy import
(CO2 emissions derived from production of energy offsite), whilst not emitted from the
refinery itself, are still important when considering the impact of the refinery operations.

Figure 2 shows the CO2 emissions profile for two typical 100 000 bpsd refineries, one
hydrocracking based, the other based on fluid catalytic cracking (FCC). Both refineries
are designed to produce EU specification products.

Figure 2: Refinery sources - total

53% 44%
HCK Process FCC Process
HCK heaters FCC heaters
23%
16% Utilities
Utilities

16% 15% 20%

Hydrogen Power Hydrogen 13%
Plant @34% Plant Power
@34%

Basis: 100,000 BPSD Arab Light

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Figure 2 indicates that:

• Emissions are dominated by those resulting from burn of fuel in fired heaters
(approximately 50%) and in utility boilers.
• The profiles for the two different types of refinery are remarkably similar, with
emissions from the hydrogen plant for the hydrocracking refinery matching those from
the FCC in the catalytic cracking refinery.

For these example profiles an efficiency of 34% has been used to calculate the CO2
emissions derived from shadow power import. However, power generating efficiency can
be as high as 70% with CHP systems, which if all power were generated on site in this
way, the overall refinery CO2 emissions could be reduced by around 7%.

In practice, the refinery will have a large number of process heaters scattered around the
site. This makes CO2 capture difficult, extremely expensive or even impractical.
However, there is potential for capture of the CO2 produced from power generation,
hydrogen production and utilities, which represents approximately half the refinery CO2
emission.

In addition, gasification can be used to provide utilities and hydrogen, whilst at the same
time allowing a single point source for CO2 capture.

Refinery issues, CO2 and the role of gasification

Two issues which influence the refinery CO2 production are;

• Fuel replacement
• The need for hydrogen

Fuel Replacement

In recent years many refiners have switched some refinery fuel needs away from heavy,
high sulphur fuel oil towards refinery fuel gas/natural gas.

The driving force for this switch has been SO2 reduction. However, it can be seen from
Figure 3 that even switching totally from heavy fuel oil to natural gas has a relatively small
impact on CO2 emissions (20% reduction). The use of hydrogen-rich fuel can reduce CO2
but again would be prohibitively expensive and impractical to implement on an existing
refinery.

In addition on many refineries, striving to manufacture low sulphur, high quality

transportation fuels hydrogen is a valuable product in its own right.

Figure 3: Fuel molecular weight and CO2 emissions

0.30
t/hr CO 2 Per MWth Fired

0.25

0.20

0.15
Fuel Oil
Natural Gas

LPG

0.10

0.05

0.00
H2 Rich 20 40 60 80 100 120
Fuel Gas
Fuel Molecular Weight
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The Hydrogen Dilemma

The demand for hydrogen on the refinery continues to grow because of:

• The tougher specifications for sulphur content in transportation fuels, resulting in

increased hydroprocessing of products.

• Processing of cheaper, higher sulphur crudes which again increases the need for
hydroprocessing.

• The introduction of residue upgrading technologies which require hydrogen in the

primary conversion process (hydrogen addition technologies) or for product
stabilisation, sulphur reduction (carbon rejection technologies).

Many refiners have recognised the value of hydrogen and the need to optimise its use
through techniques such as hydrogen pinch analysis. However, often additional
hydrogen production is unavoidable, resulting in a significant increase in CO2 on the
refinery. If the refinery is subject to CO2 bubble legislation this CO2 may need to be
captured or CO2 reductions achieved elsewhere to compensate.

Approximately 10 tonnes of CO2 per tonne of hydrogen is produced, irrespective of the

manufacturing process used (ie steam methane reforming of natural gas or gasification of
heavy residues).

However, the CO2 produced in the hydrogen production processes can be captured
relatively easily and be sequestrated or utilised.

The role of gasification

Gasification has many potential benefits to the refiner which have been widely reported in
the literature and gasification conferences worldwide.

In terms of a CO2 management strategy gasification has a significant contribution to

make, for example;

• As discussed above, gasification offers the opportunity to capture CO2 in a single

location by utilising relatively simple amine-based CO2 scrubbing technology.

• Gasification is a clean, highly efficient route to power (IGCC) and hydrogen.

Efficiency gains translate, of course, into energy savings and subsequent reduction in
CO2 emissions.

• Opportunities could exist for integration and synergy with other industries who can
use gasification syngas or gasification products and by-products.

• Gasification can allow the refiner to exit unprofitable fuel oil markets and also
decrease production of heavy fuel oil. one of the major generators of CO2.

• Through the development gas-to-liquids (GTL) technologies, gasification syngas

could be used to selectively produce diesel, the transportation fuel much in demand.

• CO2 enhanced oil recovery gives potential for greatly increased oil production from
existing oil fields. In some cases this production increase can be 20 % or higher.
However, timing is critical and some fields (for example, mature N. Sea) are rapidly
reaching the stage where enhanced oil recovery benefits tail off.

There has been an upsurge in interest in gasification technology over the last decade as
costs have fallen and low value refinery residuals become more of a problem.

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The capital cost of IGCC has fallen from around 2000-3000 $ per kW in the early 1990s
to around 1000$ per kW today. This reduction in capital cost, has resulted from a number
of factors and developments, including;

• Improved project management

• Use of standardised components
• Reduction in construction schedule
• Better air separation plants
• More efficient gas turbines
• Improved process configurations with targeted, sensible levels of integration

Gasification is also being seen as a process which offers integration and synergy
opportunities both inside and outside the refinery fence. This is because of the wide
range of hydrocarbon feeds that can be gasified and the large range of potential products
that can be produced.

Figure 4: Potential gasification feeds and products

Potential Feeds Potential Products

Natural Gas Oxygen
Nitrogen
Refinery Gas Argon
Carbon Dioxide
Residual Oils Sulphur/Sulphuric Acid
Steam
Orimulsion
Hot Water
Petroleum Coke
Combined
Electric Power
Sewage Sludge Cycle
Gasification
Waste Oils Plant Hydrogen
Carbon Monoxide
Biomass Chemical Fertilizer (Ammonia, Urea, Ammonium Nitrate)
Slag for Production Industrial Chemicals
Black Liquor Construction Methanol/Ethanol/DME
Materials or Acetic Acid, Acetic Anhydride
Municipal Solid Waste Metals Recovery
Hazardous Waste
Naphtha
Fischer-Tropsch Diesel
Coal
Synthesis Jet Fuel
Wax

Figure 5: Areas offering potential synergy and integration

Low value refinery

Gasification

Enhanced Oil CO2 H2 Refinery Needs

Recovery H2 Pipeline
Tax trading Local Needs
Bottled Gas Fuel Cells
Horticulture Hydrogen economy
Corrosion Control Petrochemicals
Steel (DRI)

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An integration example

The Queensland Clean Fuel Project (QCFP) in Australia is commercial example of a

project taking advantage of integration synergies within the refinery and over the refinery
fence.

The project was implemented through a co-ownership agreement between BP, BOC and
the Bulwer Island Energy Partnership (BIEP).

The main aim of this project, commissioned in 2000 is to increase the production of high
quality transportation fuels at the Bulwer Island Refinery.

Although based on natural gas partial oxidation, the concept is just as applicable to
gasification projects based on refinery residuals feedstock.

At QCFP there are two main areas of integration (Figure 6):

• A BOC gases complex which sells the industrial gases from the Air Separation Unit
and bottled CO2 originating from the partial oxidation unit. The Gases Complex also
provides nitrogen and oxygen to BP Bulwer Refinery where the oxygen is used to
enrich regeneration air on the FCC unit, thereby debottlenecking the unit.

• The refinery is able to supply and receive utilities from a cogen power facility and the
partial oxidation unit.

Figure 6: QCFP - an integrated gases solution

Liquid Argon
Air Liquid N2 BOC gases
ASU Gas sales
Liquid O2 Complex

Compressed H2
CO 2
N2 O2 for FCC

Natural gas
POX
BP Oil Refinery

Steam /
MWe
Demin water
Cogen
Grid

Further details on this project can be found in a paper given at the NPRA 2001 Annual
Meeting, New Orleans, March 18-20, 2001 entitled “Industrial Gas and Technology
Solutions for Clean Fuels and Lower Refinery Emissions”.

CO2 sequestration
CO2 sequestration for enhanced oil recovery (EOR) offers an exciting opportunity for both
upstream and downstream oil businesses. Enhanced oil recovery is able to extend the
useful life of oil fields increasing production significantly. Many refiners and refinery
clusters are located on or nearby coasts and many are near operating oil fields.

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The upstream sector would clearly benefit from additional oil output. Examples of benefits
for the refiner include:
• A share in upstream revenues from the incremental oil production from EOR.
• CO2 trading across national boundaries

CO2 sequestration projects will face many obstacles before implementation, not least;
• Designing a practical, cost-effective CO2 gathering infrastructure
• Bringing together, upstream and downstream businesses (which may not be in the
same company) and agreeing equitable commercial terms.
• Project timing to maximise the production benefits of EOR and meeting the refineries
CO2 reduction needs.

However, the economic drivers attached to increased oil production and substantial CO2
reduction could act as catalysts to implement projects.

Conclusions
Oil companies and refiners are actively addressing the CO2 impact of their operations and
it is expected that refiners will come under increasing pressure to reduce and / or capture
CO2.

Process heater “ end of pipe” solutions are expensive and on most refineries impractical
to implement. However, on typical FCC and hydrocracker based refineries gasification of
low value refinery residuals could be used to raise utilities and hydrogen, allowing the
relatively easy capture of half the CO2 emissions on the refinery.

Once captured the CO2 could have value as an upstream enhanced oil recovery material
sequestrated or used to enhanced greenhouse crops production. CO2 capture and
utilisation in this way may also provide CO2 trading benefits to a refiner / nation.

When considering a gasification scheme, the refiner should be aware of and open to
integration / synergy opportunities in the refinery and over the refinery fence.

So, is CO2 a perplexing problem or a real opportunity?

There is no generic gasification/CO2 reduction strategy for all refineries. Each refinery will
have its unique requirements and set of constraints. However, Foster Wheeler is well
placed to help the refiner find the optimum solution using a suite of tools based on
advanced LP modelling.

Author information
Graham Phillips is Technology Manager Refining / E Hemisphere for Foster Wheeler
Energy Limited, based in Reading, UK. He has occupied many varied positions in the
refining industry having worked for Burmah-Castrol, Natref of South Africa, BP and UOP
prior to his present appointment. Graham has authored many papers over his 30 years in
the industry. He holds a BSc in Chemical Engineering from the University of Manchester
Institute of Science and Technology and an MBA from the University of Warwick.

Foster Wheeler Energy Limited

Shinfield Park
Reading, RG2 9FW
Berkshire, UK
email: Graham_Phillips@fwuk.fwc.com

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