Tomoki Kayukawa's Presentation

Copyright 2016 JGC all rights reserved

Characterization and Refinery Processing of

Partially-upgraded Bitumen

CCQTA-COQA Joint Meeting in Edmonton, 2016

Tomoki Kayukawa JGC Corporation

1


Outline

Background Properties of Partially Upgraded Product Characterization Olefin Saturation by Hydrotreating Olefin Analysis

Refinery Processing Compatibility Test Heat Exchanger Fouling Desalting Performance

Summary 2


Heavy Oil Transportation

Well Refinery Pipeline

3

Diluent

・ Diluent shortage ・ High diluent price Dil-Bit

Dilution

・ Complex scheme ・ Large oil field

Full Upgrader Sweet SCO

・ Simple scheme ・ No diluent Partial

Upgrader Sour SCO


Partial Upgrading of Bitumen

Advantage over Dilution Diluent cost can be reduced Pipeline size can be reduced Environmentally safe (diluent easily

vaporized) Advantage over Full Upgrading Lower capital cost Smaller foot print Smaller by-product 4


Ongoing Partial Upgrading Project

5

Process (Licensor) Process type

CCU (UOP) RFCC

HTL (Ivanhoe) Thermal (Coking)

IYQ (ETX) Thermal (Coking)

HI-Q (MEG) Thermal + SDA

Eureka (Chiyoda) Thermal

HSC (TEC) Thermal

SDA (KBR) SDA

SCWC (JGC) Thermal + Extraction

Many partial upgrading technologies are existing

Most of them are thermal cracking and/or extraction (SDA)


Properties of Partially-upgraded Bitumen SCO produced by thermal cracking and extraction (5BPD scale pilot plant, SCO yield : ~70vol%)

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METHOD UNIT UpgradedBitumen TARGET

1H-NMR wt% 3.67 <1.0

DENSITY ASTM D4052 g/ml 0.9166API - o 22.9 > 19

@ 10C (Calc.) ASTM D7042 cSt 32.1 < 350

Sulfur ASTM D4294 wt% 3.23

SATURATES wt % 37.2AROMATICS wt % 37.3

POLARS wt % 9.9ASPHALTENE ASTM D4055M wt % 0.05

-360oC wt% 55360-540oC wt% 41

540oC+ wt% 4ASTM D4530 wt% 0.5ASTM D664 mg KOH/g 2.87

UOP326 g I2/100g 1.94

ASTM D2007MTYPEANALYSIS

TANDIENE VALUE

SIMDIS ASTM D2887

ANALYSIS

SPECIFICGRAVITY

MCRT

OLEFIN

ELEMENTALANALYSIS

KINETICVISCOSITY


Properties of Partially-upgraded Bitumen

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0

100

200

300

400

500

600

700

0 20 40 60 80 100

Boi

ling

poin

t [de

gC]

Fraction [wt%]

10wt% 49wt%

200degC

343degC

Fraction BP Yield wt%Naphtha IBP-200 10Distillate 200-343 39

HGO 343+ 51

SCO produced by thermal cracking and extraction (5BPD scale pilot plant, SCO yield : ~70vol%)


Objectives of Study

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Investigate product quality of partial upgrading Characterization Olefin Saturation by Hydrotreating Olefin Analysis

Address refinery issues in processing partially

upgraded oil Refinery Processing Compatibility Test Heat Exchanger Fouling Desalting Performance


Characterization

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• Olefin Saturation by Hydrotreating • Olefin Analyses


Olefin Saturation by Hydrotreating

Target olefin content: < 1.0wt% (1H-NMR) Less hydrogen consumption Less cracking, less desulfurization, less saturation of aromatic compounds Maximize liquid yield

Test unit : bench scale hydrotreating (packed

bubble column reactor, 30cc of catalyst)

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Product Quality

Target olefin content was achieved at all conditions

Lower desulfurization and aromatic saturation were observed at lower temp.

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Feedstock Product

ReactorWABT

LHSV1H-NMROlefin

Sulfur De-sulfurization

Aromatics AromaticsSaturation

degC 1/hr wt% wt% % wt% %Feedstock - - 3.67 3.2 37.3 -

RUN 1 BASE-25 BASE x 0.5 0.78 2.6 19.3 - -RUN 2 BASE BASE 0.79 2.3 28.0 36.8 1.2RUN 3 BASE+25 BASE x 2 0.82 1.9 41.0 35.1 5.8RUN 4 BASE+50 BASE x 3 0.63 1.6 50.3 33.5 10.1

RUN No.


Fraction Yields

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0

100

200

300

400

500

600

700

0 20 40 60 80 100

Boi

ling

poin

t [de

gC]

Fraction [wt%]

Feedstock

RUN 2 Product

Distillation curve does not change

FEEDSTOCK

RUN 2PRODUCT

Fraction BP Yield wt% Yield wt%Naphtha IBP-200 10 11Distillate 200-343 39 39

HGO 343+ 51 50


Conversion %

Naphtha 77.2

Distillate 74.2

HGO ≒100

00.5

11.5

22.5

33.5

44.5

Feedstock 15-B14-Product(R02, R03, R04)

Ole

fin [w

t%]

LossNaphthaDistillateHGO

3.67wt%

0.80wt%

Olefin in naphtha and distillate fraction was drastically reduced

Olefin Conversion in Fraction

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Detail Analysis for Olefin in Naphtha

Naphtha(IBP-200℃): GCxGC, TOF-MS Alkenes Diene/Cycloalkenes

Alkenes in naphtha were reduced significantly Diene/Cycloalkenes were reduced only close

to 50% 14

0

1

2

3

4

5

C5 C6 C7 C8 C9 C10 C11 C12 C13 C14

wt%

Before Hydrotreating

After Hydrotreating

0

1

2

3

4

5

C5 C6 C7 C8 C9 C10 C11 C12 C13 C14w

t%


After Hydrotreating


Detail Analysis for Olefin in Distillate

Distillate (200-343℃): HPLC, GCxGC, TOF-MS Alkenes Diene/Cycloalkenes

Alkenes in distillate were reduced significantly Diene/Cycloalkenes slightly increased. Cycloalkenes were formed by hydrogenation of aromatics??

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0.0

0.1

0.2

0.3

0.4

0.5

C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21

wt%


After Hydrotreating

0.0

0.1

0.2

0.3

0.4

0.5

C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21w

t%


After Hydrotreating


Characterization of Olefin

Olefin target (<1.0wt%) can be achieved at various operating conditions.

Lower temperature would be preferred to reduce hydrogen consumption.

Olefin is concentrated mostly in naphtha. Alkenes in naphtha and distillate were reduced

significantly by hydrotreating

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Refinery Processing

• Compatibility Test • Heat Exchanger Fouling • Desalting Performance

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Test Method for Compatibility Test

Test Method : Wiehe’s oil compatibility model IN: Insolubility number SBN: Solubility blending number

Blending partially-upgraded Bitumen (SCO) with WCS

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Total Insolubles

Blended samples were compatible at any ratios. 19

0

20

40

60

80

100

0 20 40 60 80 100

SBN

mix

, IN

Blending ratio of SCO [vol%]

SBNmix

IN

WCS SCO

IN 33.1 0

SBN 93.34 65.52


Test Method for Fouling Evaluation

Test unit : Alcor unit Test conditions : 400℃, 4 hours Criterion for fouling

[Defined by Brons, (400℃, 3hours)] Low fouling : ΔT < 15℃ Medium fouling : 15℃ < ΔT < 30℃ High fouling : ΔT > 30℃ [Defined by Shell Canada, (400℃, 4hours)] Low fouling : %F < 23%

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Schematic diagram of experimental unit

Equipment for Fouling Evaluation

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TC1 (Inlet) TC2 (Outlet) TC3 (Heated Tube) TC4 (Room Temp)

PUMP

Heating Section

Spent Sample

Fresh Sample

Heater Tube

Outlet Temp (To)

Inlet Temp (Ti)

Movable TC (Ts)


0

50

100

150

200

250

300

350

400

450

0 15 30 45 60 75 90 105

120

135

150

165

180

195

210

225

240

255

270

285

300

315

330

345

Tem

pera

ture

, T (º

C)

Elapsed Time (min)

Tc1Tc2Tc3Tc4

Temperature Trend during Test

ΔT=10℃ is defined as low fouling

ΔT = 10ºC

280ºC

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270ºC

Sample: SCO before hydrotreating


Test Method for Desalting

Test Method : Mixing and Settling Test Sample : 20ml of water and 80ml of oil pH 5~8

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Pictures during Settlement

1 minute 5 minutes

Separation was carried out within 5 minutes at various pH.

Water in oil were 0.18~0.25%. 24

Sample: SCO before hydrotreating


Conclusion

<Characterization> Olefin target can be achieved by hydrotreating. Olefin is concentrated mostly in the naphtha. <Refinery Processing> No problem was found for blending, fouling

tendency or desalting performance with SCO before hydrotreating.

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This study will be continued for understanding about quality of cracked products


Acknowledgement

This study was consulted by OMNICON Consultants Inc..

Hydrotreating, heat exchanger fouling tests and analytical works were performed by CanmetENERGY.

Detail analysis of olefins was performed by NHMFL at FSU.

Desalting test was performed by Nalco Champion.

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Test Method for Storage Stability

Test Method : ASTM D4625 (Accelerated Stability Test)

Conditions: 43.5℃ for 24 weeks

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Total Insolubles

Total insoluble increased with the time. But leveled off after 12 weeks

0

10

20

30

40

50

60

70

80

90

100

0 5 10 15 20 25 30

Tota

l Ins

olub

les

[mg/

100m

l]

Weeks

長期貯蔵安定性(ASTM D4625)

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Storage Stability

Tomoki Kayukawa's Presentation

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