ASPHALTENE CHARACTERIZATION

Criterion 2013 Ebullated Bed

Residue Upgrading Workshop

June 24, 2013

William Reppart
Regional Manager – Analytical Chemistry

Shell Global Solutions (US) Inc. May 2013 1

DEFINITIONS AND CAUTIONARY NOTE

Resources: Our use of the term “resources” in this announcement includes quantities of oil and gas not yet classified as Securities and Exchange Commission of the United States
("SEC") proved oil and gas reserves or SEC proven mining reserves. Resources are consistent with the Society of Petroleum Engineers 2P and 2C definitions.

The companies in which Royal Dutch Shell plc directly and indirectly owns investments are separate entities. In this announcement "Shell", "Shell Group" and "Royal Dutch Shell" are
sometimes used for convenience where references are made to Royal Dutch Shell plc and its subsidiaries in general. Likewise, the words "we", "us" and "our" are also used to refer to
subsidiaries in general or to those who work for them. These expressions are also used where no useful purpose is served by identifying the particular company or companies.
"Subsidiaries", "Shell subsidiaries" and "Shell companies" as used in this announcement refer to companies in which Shell either directly or indirectly has control, by having either a
majority of the voting rights or the right to exercise a controlling influence. The companies in which Shell has significant influence but not control are referred to as "associated
companies" or "associates" and companies in which Shell has joint control are referred to as "jointly controlled entities". In this announcement, associates and jointly controlled entities
are also referred to as "equity-accounted investments". The term "Shell interest" is used for convenience to indicate the direct and/or indirect (for example, through our 23 per cent.
shareholding in Woodside Petroleum Ltd.) ownership interest held by Shell in a venture, partnership or company, after exclusion of all third-party interest.

This announcement contains forward looking statements concerning the financial condition, results of operations and businesses of Shell and the Shell Group. All statements other than
statements of historical fact are, or may be deemed to be, forward-looking statements. Forward-looking statements are statements of future expectations that are based on
management's current expectations and assumptions and involve known and unknown risks and uncertainties that could cause actual results, performance or events to differ materially
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"project", "risks", "seek", "should", "target", "will" and similar terms and phrases. There are a number of factors that could affect the future operations of Shell and the Shell Group
and could cause those results to differ materially from those expressed in the forward looking statements included in this announcement, including (without limitation): (a) price
fluctuations in crude oil and natural gas; (b) changes in demand for Shell's products; (c) currency fluctuations; (d) drilling and production results; (e) reserves estimates; (f) loss of
market share and industry competition; (g) environmental and physical risks; (h) risks associated with the identification of suitable potential acquisition properties and targets, and
successful negotiation and completion of such transactions; (i) the risk of doing business in developing countries and countries subject to international sanctions; (j) legislative, fiscal
and regulatory developments including regulatory measures addressing climate change; (k) economic and financial market conditions in various countries and regions; (l) political
risks, including the risks of expropriation and renegotiation of the terms of contracts with governmental entities, delays or advancements in the approval of projects and delays in the
reimbursement for shared costs; and (m) changes in trading conditions. All forward looking statements contained in this announcement are expressly qualified in their entirety by the
cautionary statements contained or referred to in this section. Readers should not place undue reliance on forward looking statements. Additional factors that may affect future results
are contained in Shell's 20-F for the year ended 31 December 2011 (available at www.shell.com/investor and www.sec.gov ). These factors also should be considered by the reader.
Each forward looking statement speaks only as of the date of this announcement, 22 February 2012. Neither Shell nor any of its subsidiaries nor the Shell Group undertake any
obligation to publicly update or revise any forward looking statement as a result of new information, future events or other information. In light of these risks, results could differ
materially from those stated, implied or inferred from the forward looking statements contained in this announcement.

Shell may have used certain terms, such as resources, in this announcement that the SEC strictly prohibits Shell from including in its filings with the SEC. U.S. investors are urged to
consider closely the disclosure in Shell's Form 20-F, File No 1-32575, available on the SEC website www.sec.gov. You can also obtain these forms from the SEC by calling 1-800-
SEC-0330.

Shell Global Solutions (US) Inc. 2

AGENDA

• Asphaltenes

• Asphaltene Determinator Method

• Applications

• Summary and Current Work

Shell Global Solutions (US) Inc. May 2013 3

TRADITIONAL CRUDE OIL MOLECULE GROUPS

Saturates

Aromatics

Asphaltenes Resins
N
S
H

Shell Global Solutions (US) Inc. May 2013 4

SARA ANALYSIS

Crude Oil Saturates

Aromatics

Resins

Asphaltenes

Shell Global Solutions (US) Inc. May 2013 5

 ASPHALTENE STRUCTURAL MODELS

π-π Stacking Supramolecular Assembly

Dickie & Yen, Anal. Chem. 1967, 39, 1847-1852. Gray et al., Energy Fuels 2011, 25, 3125–3134.
Mullins et al., Energy Fuels 2007, 21, 2785-2794.

Solvent Shells

John Schabron, Western Research Institute, Presentation to Shell, Jan. 2012.

Shell Global Solutions (US) Inc. May 2013 6

 ASPHALTENE DETERMINATOR

Method and Results

Shell Global Solutions (US) Inc. May 2013 7

 ASPHALTENE DETERMINATOR
Schabron et al., Fuel 2008 (87), p. 165

UV/Vis Detector (500 nm)

Sample
Asph
Asph
Asph
DCM/MeOH
Teflon
Cyclohexane
Heptane
Toluene
Packing
(98:2)
ELS Detector
Column
40-60 mesh ground PTFE

Solvents
1. Heptane (15 min)
2. Cyclohexane (10 min)
3. Toluene (10 min)
4. (98:2) Dichloromethane/Methanol (10 min)

Flow rate for all solvents = 2 ml/min

Sample
a. Target 2 mg sample on column, but up to
4 mg if <10% asphaltene content
b. Sample typically dissolved in DCM; toluene
for waxy samples.
c. Neat injection of liquids (e.g. crude) when
asphaltenes are very low.

Shell Global Solutions (US) Inc. May 2013 8

 TYPICAL AD PROFILES OF CRUDE OIL ASPHALTENES
10
9
 Originally developed for coking
8 applications
ELSD Relative Intensity

7
6  Toluene is usually the tallest
5
4 asphaltene peak
3
2  Derived Parameter(s):
1
0  WRI Coking Index (CI), defined
0 10 20 30 40
Elution Time
as the area ratio of ELSD
Labuan Arab Light Kaliningrad cyclohexane to DCM peaks
10 CI > 2 : no coking tendency
8 CI < 2 : likely to have coke
ELSD Relative Intensity

6
Crude Oil Coking Index
4
Labuan 5.7
2
Arab Light 5.1
0
Kaliningrad 1.9

Shell Global Solutions (US) Inc. May 2013 9

 SOLUBILITY PARAMETER RANGE FOR AD METHOD

Toluene
Relative Intensity

DCM/MeOH (98:2)
(18.1,6.4,6.4)
CylHex
DCM/MeOH

15 25 35 45
Elution Time

Toluene
(18.0,1.4,2.0)

CylHex (16.9,0,0.2)

Heptane

Shell Global Solutions (US) Inc. May 2013 10

 ANALYSIS OF AD FRACTIONS BY 13C NMR, ELEMENTAL
Unprocessed Bitumen Asphaltenes
AD AD AD
Property CylHex Tol DCM
%Aromatic carbons 50 52 55
Relative Intensity

C-C / C-H 0.9 1.1 1.0

DCM/MeOH
%Aliphatic carbons 50 48 45
Toluene
CylHex

naphthenic / alkyl 1.7 1.8 1.8

Heteroatoms (wt%) 10.3 11.8 12.4

15 25 35 45
Elution Time Drum Test Product Asphaltenes
AD AD AD
Property CylHex Tol DCM
As solvent strength increases:
%Aromatic carbons 58 83 83
 Aromaticity increases C-C / C-H 0.7 0.7 0.7

 Heteroatoms increase %Aliphatic carbons 42 17 17

naphthenic / alkyl 5.0 1.4 2.4

Heteroatoms (wt%) 8.2 9.1 11.0

Shell Global Solutions (US) Inc. May 2013 11

 ASPHALTENE DETERMINATOR

Applications

Shell Global Solutions (US) Inc. May 2013 12

PROCESS FEED CHARACTERIZATION
100

ELSD Relative Intensity

80

60

40

20

0
15 20 25 30 35 40 45
Time, shifted for clarity

Feed 1 Feed 2 Feed 3

Heptane % 97.7 95.8 94.9
Cyclohexane % 1.2 1.2 2.1
Toluene % 1.0 2.8 2.9
DCM/MeOH % 0.07 0.15 0.10
Heptane Insolubles % 2.3 4.2 5.1
Coking Index 18 9 21

Shell Global Solutions (US) Inc. May 2013 13

PROCESS MONITORING

Conversion Level AD Coking Index vs. Process Severity

10
60

1 Feed
40
Run 2-1
0.1
run 2-2
12
0.01 run 2-3

0
0.001

Coking Index: 7.0 0.06 0.02 0.01

Vanadium: 185 200 >200
C7 Asphaltenes: 13.2 13.7 16.4

Shell Global Solutions (US) Inc. May 2013 14

 CATALYST MONITORING

Feed Product WP4 Product WP23

Property TLP 680+ 1000+ TLP 680+ 1000+
Heptane % 95.8 99.4 99.1 97.7 98.6 98.1 95.3
Cyclohexane % 1.2 0.00 0.01 0.03 0.01 0.02 0.08
Toluene % 2.8 0.5 0.8 2.0 1.1 1.6 4.0
DCM/MeOH 0.15 0.14 0.15 0.32 0.28 0.29 0.66
Heptane Insolubles % 4.2 0.6 0.9 2.3 1.4 1.9 4.7
Coking Index 9 - 0.06 0.09 0.03 0.09 0.11

Shell Global Solutions (US) Inc. May 2013 15

 SUMMARY

• The Asphaltene Determinator method:

• Provides detailed analysis of asphaltenes in hydrocarbon streams

• Uses very little sample and provides results in one hour or less

• It can be used for:

• Process design and monitoring

• Feed and product characterization

• Catalyst monitoring

Shell Global Solutions (US) Inc. May 2013 16

 CURRENT WORK

Shell development efforts

focused on extending the AD
analysis to include:
• Molecular weight (using
SEC)
• Solubility parameters
(using RI)

Gwenaëlle James Robert

Philibert Nguyen Szentirmay

Shell Global Solutions (US) Inc. May 2013 17

 Q&A

Shell Global Solutions (US) Inc. May 2013 18