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

Control of Catalyst Deactivation in THAI-CAPRI Process for In-Situ

Oilsand Recovery and Upgrading

Paper Reference: WHOC12-129

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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)

Conclusions and future work

Use of guard bed to control deactivation by coking Effect on API gravity and viscosity reduction Effect on coke content

Deposits in reactor

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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

Advancing Combustion Front

Mobilised Fluid

Annular Catalyst ToeHeel

Enriched Air and steam

Producer Well

Combustion frontMobile Oil Zone

(MOZ)

Cold Heavy Oil

Thermal cracking

Catalytic cracking in situ

Reservoir formation

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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

Glass beads

Furnace

Vent or to RGA

Gas-Oil Disengagement

Light oil

N2 or THAI gas

Feed oil

Catalyst bed

Reactor

Glass beads

Well

Section Through Pipeline

Oil

Gravel-Packed Catalyst

Fixed-bed reactor

Experimental model of the CAPRI section

Field scale representation of the CAPRI section

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

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POSSIBLE REACTION PATHWAYS

Heavy oilHeavy oil

Synthesis

light oil

Synthesis

light oil

CokeCoke

GasesGases

Desired product

By- product

By-product

Feed oil

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 CRACKINGTemp. (oC) ΔoAPI350 0.7

400 1.1

425 1.7

Temp. (oC) DVR (%)350 24

400 40

425 51

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

DVR = (µo-µ)/µo x 100 %

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CATALYST CHARACTERISTICS

CatalystName

Average pore diameter

(Å)

BET surface area (m2/g )

Co-Mo 84.01 214.10

Ni-Mo 123.63 195.41

Using ASTM C1274 (Brunauer – Emmett – Teller, BET)

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MATERIAL BALANCE

Effect reaction temperature

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CATALYTIC UPGRADING Effect of reaction temperature on API gravity

Temp. (oC): 350 400 425

ΔoAPI: 1.7 2.3 3.8

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CATALYTIC UPGRADING Effect of reaction temperature on viscosity

Temp. (oC): 350 400 425

DVR (%): 47 67.4 81.9

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CATALYTIC UPGRADING Simulated distillation of feed and upgraded oil using American Society for Testing and Materials, ASTM-D2887 (Agilent 6850N gas chromatograph)

The curves shift to the left

indicate improved yield in distillates

at low temperature

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WHSV (h-1) ΔoAPI9.1 5

13.6 4

21.8 3

WHSV (h-1) DVR (%)9.1 85

13.6 82

21.8 79

EFFECT OF WHSV ON CATALYTIC UPGRADING

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

The curves shift to the left indicate

improved yield in distillates at low

temperature

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DEPOSITS IN THE REACTOR

Possible deposits may be asphaltenes, coke and metals.

They cause catalyst deactivation and shorten lifetime during upgrading.

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USE OF ACTIVATED CARBON AS GUARD BED

Glass beads

Guard bed

Feed oil and gas

Catalysts bed

Glass beads Gas

Oil

Gas-oil separator

Properties of Activated Carbon

Surface area (m2/g) 820

Pore diameter (Å) 30

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USE OF GUARD BED

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CATALYST DEACTIVATION BY COKING

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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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[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 high-viscosity 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.

REFERENCES

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

Thank you

Paper Reference: WHOC12-129

Questions?

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THERMOGRAVIMETRIC ANALYSIS OF THE ACTIVATED CARBON GUARD BED