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Size of the anions in ionic liquids affect the extraction efficiency !!! Size of the anion ... Molar concentration of HCl. [HC1im]Cl+10%H2O. EMIM-DEP. 0. 5. 10. 15.

Unconventional Methods for the Demetalation of Bitumen Garima Chauhan*, Arno de Klerk Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G 2V4, Canada

Scope of the work Crude Oil

Vanadium: 180-250ppm Nickel: 80-124 ppm Feed Preparation

Residue

Distillation

(Dewatering/ Desalting)

Thermal/hydro cracking

Demetalation

Unconventional Methods for Metal Recovery

Ionic Liquids

Photo-irradiation Electro-chemical Reaction

Ionic Liquid Assisted Metal Extraction Hypothesis-1: Equilibrium Assisted Extraction !!!

Ionic Liquid

Demetallized crude oil Dilbit Sample

Further Downstream Processing Metal Loaded Ionic Liquid

Extractor Separator

Displacement Equilibria

Ionic Liquid Recovery

+

A-X

+

X

A-M

Electrochemical Separation

Hypothesis-2: Size of the anions in ionic liquids affect the extraction efficiency !!!

Nomenclature - M : Metal ion, A-X : ionic liquid, X : Ion responsible for the displacement of metal ion from porphyrin ring

Hypothesis-3: Acid Saturated Ionic Liquid Increases Metal Recovery !!! 35

Size of the anion (%) Metal Extraction from Bitumen

8 6 4

Solvent Recovery Demetallized crude oil

Further Downstream Processing

25 20 15 10 5

0

0 2 4 6 8 Molar concentration of HCl

10

[HC1im]Cl+10%H2O EMIM-DEP

30

2 0

Photo-irradiation Assisted Metal Recovery Solvent (2-Propanol)

[HC1im]Cl+10%H2O EMIM-DEP

10

% Ni Recovery

a) 1-Ethyl-3-methylimidazolium chloride (b) 1-Ethyl-3-methylimidazolium thiocyanate (c) 1-Ethyl-3methylimidazolium hydrogen sulfate (d)1-Ethyl-3-methylimidazolium diethyl phosphate

% V Recovery

12

0

2 4 6 8 Molar concentration of HCl (M)

10

Hypothesis: Photo-dissociation in presence of hydrogen donating solvent convert the ‘bound’ type metalloporphyrins into ‘free’ type porphyrins which consequently results into significant extraction of metals.

Photoreactor

hν HCl Solution

Extractor

Electrochemical Recovery of Metals

Separator Metal loaded HCl solution

Metal in Residue Form

Hydrogenation in presence of hydrogen donor solvent

Hypothesis: Electrochemical treatment in presence of a protonating solvent results into the release of free prophyrins. It can be employed in conjunction with solvent extraction to develop a novel effective demetalation process.

VO3-

hν, O2

Acknowledgement: *Presence of Soret band after the electrochemical treatment validates that porphyrins are not destroyed during the electrolysis process.

The authors would like to thank Alberta Economic Development & Trade (Project No: AB EconD&T 2510-20161207) for the financial support. Research Work is being carried out at : Department of Chemical & Materials Engineering, Laboratory : 5-112, 9211 - 116th Street University of Alberta Edmonton, AB, T6G 1H9 CANADA

Team Members: Dr. Garima Chauhan ([email protected]) Dr. Arno de Klerk ([email protected])