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Hydrothermal Technology for recovery of Molybdenum from

spent Hydro-Treating catalysts. Wilfred van WijkRob van der Meij

December 3, 2014

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Rob van der Meij• Serial Entrepreneur in

Clean Tech• > 25 years in catalyst, water

and chemical industry• Akzo Nobel, Cap Gemini,

Shell Chemicals• 7 years Start Ups

Catalysts, Biofuels, Water, Separations

• KiOR, fluXXion, BiAqua, Hermes Catalysts, HyVent

• Chemical Engineer TU Delft, NL

Wilfred van Wijk• > 20 years in

Organophosphorus, Specialty monomer, Organics, Chemical by-and waste streams and general chemical industry• CYTEC Industries

Phosphine and derivatives• 5 years providing

chemistry, chemical and technology solutions; HyVent, Gulf Interchem, ICSP.

•Chemist, University of Leiden, NL

December 3, 2014

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HyVent Technology

Core Technology ⇨ HydroThermal treatment

Testing facilities in The Netherlandsand Germany

December 3, 2014

Processes in the sub- or

super- critical regime of

water

4

HyVent Technology application areas

Synthesis

OxidesFerrites Heavy Oil Upgrading

BitumenVacuum Resid

Removal of metals

Spent refinery catalystsMixed oxides

Destruction

Toxic wastesOrganic/Inorganic mixturesHigh COD

water

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Historical Molybdenum (Mo) pricing

Hydroprocessing Catalyst contain 15-25% MoO3

MoO

3 pr

ice

(USD

/lb)

?

YearDecember 3, 2014

Historical pricing 2.5 $/lb

Spent hydrotreating catalysts are both a hassle and a source of value

for refiners

Co-Mo Ni-Mo

160,000 tpaRemove S from oil

Legal waste disposal

obligation

Hazardous waste

>20% metalsLargely Mo

20 % Carbon and Sulfur

Needs to be removed prior to processing

Metals value 4000 $/ton

Needs to be removed prior to processing

Export Documentation and transport

hassle

Liability risk when done incorrectly

December 3, 2014 6

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High costs in metal recovery value chain limits return to

refiner

Unload spent catalyst

Special packaging

Roaster for C,S removal

Metal reclaim

> 65% generated in North America, Europe, Middle East

> 65% reclaim capacity in Asia

⇨ Large transport volumes, Export chemical waste

• Large facilities

• Roasting and metal reclaim often not at same site

⇨ Multi-step location, international processing, documentation hassle

Total costs > $ 2500 /ton

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Current metal recovery technologies for Mo and V have

serious limitations• Roasting for Carbon and Sulfur removal

– Environmentally unfriendly– High capital investment, High maintenance

• Pyro metal recovery– Smelting of material in electronic furnaces– yielding Ferro-alloys used in steel industry, no re-use for catalysts– Low recovery value (alloy)– High capital investment, High energy consumption

• Hydrometallurgical metal recovery– Chemical leaching with acid or base materials– Complex processing with many contamination limitations– Environmentally unfriendly waste waters

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HyVent’s Integrated Processing Scheme

• Hydrothermal dissolution ofC, S and metals

• Destruction of organic compounds

• Combination of proven processes from catalyst and battery recycle industry

• Zero Liquid Discharge process• High recovery value for M and V

Hydrothermal processing Metal Recovery

Spent Catalysts

Water

energy

CO2, N2

Metal salts

solids

Integrated Metal Recovery Process

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The HyVent process is environmentally friendly

No waste water or NOX and SOX emissions

feed

grind

mill

mix

HP Pump

HT Reactor

treatment + leaching

depressurize

centrifuge

Solids collection

Mo recovery

Water treatment

Alumina/Ni/Co cake

liquids

Molybdenum salt

Clean water for re-use

Salts for disposal

Pretreatment Reactor Separation Recovery

Additives

Water

Spent Catalyst V- recovery Vanadium salt

December 3, 2014

Solids

Liquids

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HyVent uses all commercially proven equipment

All stackable, modular container

framed & sized equipment

Tubular Hydrothermal

Reactor system

Slurry of un-regenerated

catalyst prior to

hydrothermal treatment

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HyVent’s process has strong advantages

Current Processes

Large, fixed unitsHigh CAPEXMulti-location process:

- Roasting separate from metal recovery- multi transport, non-local- export

Metal recoverypyrometallugy ⇨ ferro-alloy (low value)hydrometallurgy ⇨ large acqueous waste volumes

Gas emissionsSulfuroxides, CO2, NOx and C-compounds

HyVent Hydrothermal Process

Modular, smallLow CAPEXLocal, single location process

⇨ C & S removal in process ⇨ Local single transport

Mo and V compound as salt solutions ⇨ high value

Zero Liquid Discharge ⇨ recycle process water

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HyVent will build local, customized, modular facilities to eliminate transport

hassle and reduce costs

• Modular, containerized local facility• NO transport, NO documentation hassle• High return value for Mo and V metal recovery• Modular facility with ‘plug and play’ construction set up• Low CAPEX ⇨ 5-6 million USD per plant• ZLD processing, full water recycle, no emissions• High flexibility to adapt to local market

– Mo or Mo and V recovery– Chemical catalyst processing with other metals (Cu, Zn, RE etc.) add on

possible– Noble metal recovery scheme under development

December 3, 2014

Several 1000-4000 tpa facilities can be build around refining

centers in the world 10,300

60,000

30,000

40,000

Asia

AmericasEurope

Global hydro-processing spent catalyst generation (tons/year)

2

3

11

3

22

2

America’s, Europe, export >65 % of spent catalyst to Asia Pacific now

(VN, K, CN, TW)

# Potential number of facilities by region

1

2

2

1

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Better return to refiner with HyVent:

⇨ avg >700 $/ton over past 15 years !!

Net return difference for refinery HyVent vs competition

(current pricing)

December 3, 2014 Year (+2000)

USD

/ to

n

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Higher value return to Refinery without hassle

• Recovery of Mo reduces refinery exposure to metal price fluctuations

• Swap recovered Mo with fresh catalyst Mo

• Better value recovery for refinery

• No documentation and transport hassle for refinery

• No export waste liability risk

• Long term guaranteed off-take agreementDecember 3, 2014

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Closing remarks

The HyVent integrated HydroThermal process for treatment of spent refinery catalyst and recovery of Molybdenum offers an environmentally friendly, economic and flexible processing technology in answer to changing market demand and requirements

Thank you for your attention

December 3, 2014