Control of Catalyst Deactivation in THAI-CAPRI Process for In-Situ Oilsand Recovery and Upgrading

Authors: Abarasi Hart, Gary Leeke, Malcolm Greaves and Joe Wood

Paper Reference: WHOC12-129

OVERVIEW
 Introduction
 The THAI-CAPRI process  Objectives  Experimental section  Possible upgrading reaction  Thermal cracking  Catalytic upgrading  Catalyst characterisation  Material balance  Effect of reaction temperature  Effect of weight hourly space velocity (WHVS)  Deposits in reactor  Use of guard bed to control deactivation by coking  Effect on API gravity and viscosity reduction  Effect on coke content  Conclusions and future work
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INTRODUCTION
 Out of the world’s total oil resources of 9-13 trillion barrels, heavy oil and bitumen make up 70%[1,2,3]  In order to produce and upgrade heavy oil in situ, the Toe-to-Heel Air Injection (THAI) and the add-on CAtalytic upgrading PRocess In-situ (CAPRI) was developed[4].  The process combines in situ combustion and horizontal production well (HPW), in which catalyst incorporated around the perimeter of the HPW .  In THAI-CAPRI process small portion of the oil is burned to support in-situ combustion in order to drive thermal and catalytic conversion of heavy oil into light oil.
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THE THAI-CAPRI PROCESS
Thermal cracking
Producer Well
Mobile Oil Zone (MOZ)
Reservoir formation

Combustion front

Enriched Air and steam

Cold Heavy Oil

Advancing Combustion Front

Catalytic cracking in situ

Mobilised Fluid

Heel

Annular Catalyst

Toe

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OBJECTIVES
 To investigate the effect of - Thermal cracking effect - Reaction temperature - Weight hourly space velocity (WHSV)  To control catalyst deactivation by -The use of guard bed -The use of hydrogen -The use of steam

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EXPERIMENTAL SECTION
Field scale representation of the CAPRI section Experimental model of the CAPRI section

N2 or THAI gas

Well
Gravel-Packed Catalyst

Reactor Feed oil Furnace Glass beads
Fixed-bed reactor Oil

Section Through Pipeline

Catalyst bed

Experimental Conditions Pressure = 20 bar, Temperature = 350 to 425oC, flow rate = 1mL/min, WHSV = 9 to 21.8 h-1, Gas-to-oil ratio = 500 mL/mL

Glass beads Vent or to RGA Gas-Oil Disengagement Light oil

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POSSIBLE REACTION PATHWAYS
By-product

Gases

Feed oil

Synthesis

Heavy oil

light oil

Desired product

Coke

By- product

Long chain paraffins → gases + light paraffins

naphthenes → ring openings → straight chain paraffins/olefins
Resins → gases + light hydrocarbons + asphaltenes + coke↓ Asphaltenes → gases + light hydrocarbons + resins + coke↓
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THERMAL CRACKING
Mean API gravity (oAPI)
16 15 14 13 12 300 350 400 450 Thermal upgrading by Glass beads Feed oil

Temp. (oC) 350 400 425 Temp. (oC) 350 400

ΔoAPI 0.7 1.1 1.7 DVR (%) 24 40

Temperature (oC)
0.6

Mean viscosity (Pa.s)

0.5 0.4 0.3 0.2 0.1 0 300

Thermal upgrading by Glass beads

Feed oil

425
350 400 450

51

Temperature (oC)

ΔoAPI = Improved API – initial API DVR = Degree of viscosity reduction

DVR = (µo-µ)/µo x 100 %
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CATALYST CHARACTERISTICS
 Using ASTM C1274 (Brunauer – Emmett – Teller, BET)
Catalyst Name Average pore diameter (Å) BET surface area (m2/g )

Co-Mo Ni-Mo

84.01 123.63

214.10 195.41

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MATERIAL BALANCE
 Effect reaction temperature

100 80 Weight %

60
40 20 0 Gas (x10) Light oil Coke (x10)

350C

400C
425C

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CATALYTIC UPGRADING
 Effect of reaction temperature on API gravity
22 21 20 API Gravity (Deg) 19 18 17 16 15 14

Feed Oil

NiMo 350C

NiMo 400C

NiMo 425C

13
12 0 200 400 600 Time(min) 800 1000 1200

Temp. (oC): 350

400

425

ΔoAPI:

1.7

2.3

3.8

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CATALYTIC UPGRADING
 Effect of reaction temperature on viscosity
0.6

NiMo 350C
0.5

NiMo 400C

NiMo425C

Feed oil

Viscosity (Pa.s)

0.4 0.3 0.2 0.1 0 0 200 400 600 800 1000 1200

Time (min)

Temp. (oC): 350
DVR (%): 47

400

425
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67.4 81.9

CATALYTIC UPGRADING
 Simulated distillation of feed and upgraded oil using

American Society for Testing and Materials, ASTMD2887 (Agilent 6850N gas chromatograph)
100 90 80 70 Percentage yield (%) 60 50 40 30 20
Feed Oil Co-Mo 425C 20bar 1ml/min Co-Mo 400C 20bar 1ml/min Co-Mo 350C 20bar 1ml/min

The curves shift to the left indicate improved yield in distillates at low temperature

10
0 50 100 150 200 250 300 Temperature (oC) 350 400 450 500

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EFFECT OF WHSV ON CATALYTIC UPGRADING
20

Mean API gravity (oAPI)

WHSV (h-1) ΔoAPI 9.1 5 13.6 21.8 4 3

Feed oil

NiMo 425C

CoMo

19 18 17 16 15 14 13 12 0 5 10 15 20 25

WHSV (h-1)

Mean viscosity (Pa.s)

WHSV (h-1) DVR (%) 9.1 85 13.6 21.8 82 79

0.2 0.16 0.12 0.08 0.04 0 0

CoMo 425C

NiMo 425C

5

WHSV (h-1)

10

15

20

25

While other conditions remain constant the catalysts weight varies from 2.5, 4 to 6g

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EFFECT OF WHSV ON CATALYTIC UPGRADING
 Simulated distillation of feed and upgraded oil
120

Feed oil
100

CoMo 6g CoMo 2.5g NiMo 4g

CoMo 4g NiMo 6g

Percentage yield (%)

80

NiMo 2.5g
60

40

The curves shift to the left indicate improved yield in distillates at low temperature

20

0 30 80 130 180 230 280 330 380 430 480

Temperature (oC)

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DEPOSITS IN THE REACTOR
Mass of deposits in reactor (g)
8 7 6 5 4 3 2 1 0 350 400 425

Co-Mo

Ni-Mo

Mass of deposits in reactor (g)

 Possible deposits may be asphaltenes, coke and metals.  They cause catalyst deactivation and shorten lifetime during upgrading.

Temperature (oC)
5 4 3 2 1 0 0 5 10 15 20 25 CoMo 425C NiMo 425C

WHSV

(h-1)

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USE OF ACTIVATED CARBON AS GUARD BED
Feed oil and gas

Properties of Activated Carbon
Glass beads Guard bed

Surface area (m2/g) Pore diameter (Å)

820 30

Catalysts bed

Glass beads

Gas

Gas-oil separator

Oil

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USE OF GUARD BED
23 22 21 20 19 18 17 16 15 14 13 12
0

Feed Oil

Activated carbon (AC)

CoMo 425C

AC+CoMo 425C

API gravity (Deg.)

200

400

600

800

1000

1200

1400

1600

Time (min)
0.6 0.5

Feed Oil Activated carbon (AC) 425C

CoMo425C AC+CoMo 425C

Viscosity (Pa.s)

0.4 0.3 0.2 0.1 0 0 200 400 600 800 1000 1200 1400 1600

Time (min)

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CATALYST DEACTIVATION BY COKING
100 0.0 -1.0 -2.0 TG CoMo TG AC+CoMo DTG CoMo DTG AC+CoMo -3.0 -4.0

Weight loss (wt. %)

80 60 40 20

0
0 100 200 300 400 500 600 700 800 900 1000

-5.0

Temperature (oC) Coke content (wt. %)
70 60 50 40 30 20 10

0

CoMo

AC + CoMo

Derivative weight (%/min)

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CONCLUSIONS
 The effect of reaction temperature, WHSV and the use of guard bed on CAPRI was investigated.  It was found that the produced oil API gravity increased by ~ 2 to 7oAPI, the viscosity reduced by 42 to 82%, and distillation properties improved depending on the temperature in the range 350-425oC and WHSV.  Despite the improved upgrading at higher reaction temperature and lower WHSV, more carbon rejection leading to rapid catalyst deactivation was observed.  The use of activated carbon guard bed upstream the reactor reduced coke formation.
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FUTURE WORK
 Therefore, further investigation on controlling premature deactivation via: - Use of hydrogen - Use of steam - Catalyst modification

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ACKNOWLEDGEMENT

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REFERENCES
[1] Smalley, C. (2000) Heavy oil and viscous oil, Chapter from Modern Petroleum Technology, R. A. Dawe, ed., John Wiley and Sons Ltd. [2] Das K. Swapan and Butler M. Roger, 1998. Mechanism of the vapour extraction process for heavy oil and bitumen, Journal Petroleum Science & Engineering, 21, 43-59. [3] Zhang H.Q., Sarica C., Pereya E., 2012. Review of highviscosity oil multiphase pipe flow, Energy & Fuels, dx.doi.org/10.1021/ef300179s [4] T., Xia and M., Greaves, 2001. 3-D physical model studies of downhole catalytic upgrading of Wolf Lake heavy oil using THAI, Paper 2001-17 presented at the Petroleum Society’s Canadian International Petroleum Conference 2001, Calgary, Alberta, Canada, June 12-14.
WHOC12-129

Thank you
Questions?
Paper Title: Control of Catalyst Deactivation in THAI-CAPRI Process for In-Situ Oilsand Recovery and Upgrading

Authors: Abarasi Hart, Gary Leeke, Malcolm Greaves and Joe Wood

Paper Reference: WHOC12-129

THERMOGRAVIMETRIC ANALYSIS OF THE ACTIVATED CARBON GUARD BED
100 90

TG of Guard bed AC 425
DTG of Guard bed AC 425C

1 0 -1 -2 -3 -4 -5 -6

80

70

60
50 40 30 20 10 0 -10 0 100 200 300 400 500 600 700 800 900

-7 1000

Temperature (oC)

Derivative weight loss (%/min)

Weight loss, w (%)

WHOC12-129

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